U.S. patent application number 14/007300 was filed with the patent office on 2014-02-20 for copper-containing metal pigments with a metal oxide layer and a plastic layer, method for the production thereof, coating agent and coated object.
This patent application is currently assigned to ECKART GMBH. The applicant listed for this patent is Sebastian Hofener, Phu Qui Nguyen, Dirk Schumacher, Oliver Struck. Invention is credited to Sebastian Hofener, Phu Qui Nguyen, Dirk Schumacher, Oliver Struck.
Application Number | 20140050768 14/007300 |
Document ID | / |
Family ID | 46831749 |
Filed Date | 2014-02-20 |
United States Patent
Application |
20140050768 |
Kind Code |
A1 |
Struck; Oliver ; et
al. |
February 20, 2014 |
Copper-Containing Metal Pigments with a Metal Oxide Layer and a
Plastic Layer, Method for the Production Thereof, Coating Agent and
Coated Object
Abstract
The invention relates to copper-containing metal pigments,
wherein the copper-containing metal pigments have an elemental
copper content of at least 50 wt. %, relative to the total weight
of the uncoated copper-containing metal pigment, wherein the
copper-containing metal pigments have at least one enveloping metal
oxide layer and at least one enveloping chemically non-reactive
plastic layer, wherein the sum of the amounts of the at least one
chemically non-reactive plastic layer and of the at least one metal
oxide layer lies in a range of from 10 to 50 wt. %, relative to the
weight of the uncoated metal pigment, and the weight ratio of the
at least one metal oxide layer to the at least one chemically
non-reactive plastic layer lies in a range of from 1:2 to 1:20. The
invention furthermore relates to a method for producing these
pigments and the use thereof.
Inventors: |
Struck; Oliver; (Henfenfeld,
DE) ; Nguyen; Phu Qui; (Moenchengladbach, DE)
; Schumacher; Dirk; (Pegnitz, DE) ; Hofener;
Sebastian; (Nurnberg, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Struck; Oliver
Nguyen; Phu Qui
Schumacher; Dirk
Hofener; Sebastian |
Henfenfeld
Moenchengladbach
Pegnitz
Nurnberg |
|
DE
DE
DE
DE |
|
|
Assignee: |
ECKART GMBH
Hartenstein
DE
|
Family ID: |
46831749 |
Appl. No.: |
14/007300 |
Filed: |
March 21, 2012 |
PCT Filed: |
March 21, 2012 |
PCT NO: |
PCT/EP12/54961 |
371 Date: |
October 29, 2013 |
Current U.S.
Class: |
424/401 ;
427/388.1; 524/781 |
Current CPC
Class: |
C09C 1/66 20130101; A61Q
1/04 20130101; A61K 2800/651 20130101; C08K 9/02 20130101; C09D
7/65 20180101; A61K 2800/43 20130101; A61Q 3/02 20130101; A61K
2800/621 20130101; C09D 7/62 20180101; C09C 1/0021 20130101; C09D
7/70 20180101; A61K 8/19 20130101; A61K 2800/624 20130101; C09C
2200/405 20130101; A61K 8/0262 20130101; A61Q 1/12 20130101; A61Q
19/10 20130101; C09C 2200/1054 20130101; C09C 2200/1058 20130101;
A61Q 19/00 20130101; C08K 2003/085 20130101; A61K 8/8152 20130101;
A61Q 5/06 20130101; C09C 1/627 20130101; A61Q 1/06 20130101; A61K
2800/63 20130101; C08K 9/10 20130101; A61K 8/0258 20130101; A61Q
1/10 20130101 |
Class at
Publication: |
424/401 ;
524/781; 427/388.1 |
International
Class: |
C09C 1/62 20060101
C09C001/62; A61Q 19/00 20060101 A61Q019/00; C09D 7/12 20060101
C09D007/12; A61K 8/02 20060101 A61K008/02 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 25, 2011 |
DE |
10 2011 001 575.2 |
May 27, 2011 |
DE |
10 2011 103 882.9 |
Claims
1. A platelet-shaped copper-containing metal pigment which has an
elemental copper content of at least 50 weight percent, relative to
the weight of an uncoated copper-containing metal pigment, wherein
the copper-containing metal pigment comprises a coating comprising
at least one enveloping metal oxide layer and at least one
enveloping chemically non-reactive plastic layer, wherein the sum
of the amounts of the at least one chemically non-reactive plastic
layer and of the at least one metal oxide layer lies in a range of
from 10 to 50 weight percent, relative to the weight of the
uncoated metal pigment, and the weight ratio of the at least one
metal oxide layer to the at least one chemically non-reactive
plastic layer lies in a range of from 1:2 to 1:20.
2. The platelet-shaped copper-containing metal pigment according to
claim 1, wherein the at least one enveloping metal oxide layer is
arranged between the copper-containing metal pigment and the at
least one chemically non-reactive plastic layer.
3. The platelet-shaped copper-containing metal pigment according to
claim 1, wherein the at least one chemically non-reactive plastic
layer is arranged between the copper-containing metal pigment and
the at least one enveloping metal oxide layer.
4. The platelet-shaped copper-containing metal pigment according to
claim 1, wherein the weight proportion of the at least one
enveloping metal oxide layer lies in a range of from 0.9 to 12
weight percent, relative to the weight of the uncoated
copper-containing metal pigment.
5. The platelet-shaped copper-containing metal pigment according to
claim 1, wherein the weight proportion of the at least one
enveloping metal oxide layer in platelet-shaped copper-containing
metal pigment in which a chemically non-reactive plastic layer
forms a top layer of the coating lies in a range of from 0.9 to 12
weight percent and in platelet-shaped copper-containing metal
pigment in which a metal oxide layer forms a top layer of the
coating lies in a range of from 1.0 to 10 weight percent.
6. The platelet-shaped copper-containing metal pigment according to
claim 1, wherein the weight ratio of the at least one enveloping
plastic layer lies in a range of from 8 to 40 weight percent,
relative to the weight of the uncoated copper-containing metal
pigment.
7. The platelet-shaped copper-containing metal pigment according to
claim 1, wherein the copper-containing metal pigment is selected
from the group consisting of copper pigments, brass pigments,
oxidized copper pigments, oxidized brass pigments and mixtures
thereof.
8. The platelet-shaped copper-containing metal pigment according to
claim 1, wherein the at least one metal oxide layer is selected
from the group consisting of silicon oxide, aluminum oxide, boron
oxide, zirconium oxide, cerium oxide, iron oxide, titanium oxide,
chromium oxide, tin oxide, molybdenum oxide, oxide hydrates
thereof, hydroxides thereof, and mixtures thereof.
9. The platelet-shaped copper-containing metal pigment according to
claim 8, wherein the at least one metal oxide layer consists
substantially of silicon oxide.
10. The platelet-shaped copper-containing metal pigment according
to claim 1, wherein the at least one plastic layer consists
substantially of a plastic selected from the group consisting of
polyacrylate, polymethacrylate, polyacrylamide, polyacrylonitrile,
polyvinyl chloride, polyvinyl acetate, polyamide, polyalkene,
polydiene, polyalkyne, polyalkylene glycol, epoxy resin, polyester,
polyether, polyol, polyurethane, polycarbonate, polyethylene
terephthalate and mixtures thereof.
11. The platelet-shaped copper-containing metal pigment according
to claim 10, wherein the at least one plastic layer consists
substantially of polyacrylate, polymethacrylate, or a mixture
thereof.
12. The platelet-shaped copper-containing metal pigment according
to claim 1, wherein the at least one plastic layer consists
substantially of polyacrylate, polymethacrylate, or a mixture
thereof and in that the at least one metal oxide layer consists
substantially of silicon oxide, wherein the weight ratio of the at
least one metal oxide layer to the at least one chemically
non-reactive plastic layer lies in a range of from 1:2.2 to
1:17.
13. The platelet-shaped copper-containing metal pigment according
to claim 12, wherein the sum of the amount of the at least one
chemically non-reactive plastic layer and the amount of the at
least one metal oxide layer lies in a range of from 13 to 40 weight
percent, relative to the weight of the uncoated metal pigment.
14. The platelet-shaped copper-containing metal pigment according
to claim 12, wherein the weight ratio of the at least one metal
oxide layer to the at least one chemically non-reactive plastic
layer lies in a range of from 1:2.5 to 1:15.
15. The platelet-shaped copper-containing metal pigment according
to claim 12, wherein the weight proportion of the at least one
metal oxide layer lies in a range of from 1.5 to 9 weight percent,
relative to the weight of the uncoated copper-containing metal
pigment.
16. The platelet-shaped copper-containing metal pigment according
to claim 12, wherein the weight proportion of the chemically
non-reactive plastic layer lies in a range of from 10 to 35 weight
percent, relative to the weight of the uncoated copper-containing
metal pigment.
17. The platelet-shaped copper-containing metal pigment according
to claim 12, wherein the at least one chemically non-reactive
plastic layer is obtained by thermal polymerization.
18. The platelet-shaped copper-containing metal pigment according
to claim 12, wherein the at least one chemically non-reactive
plastic layer is obtained by initiator-induced radical
polymerization.
19. A pigmented coating agent comprising at least one
platelet-shaped copper-containing metal pigment according to claim
1.
20. A coated object comprising at least one platelet-shaped
copper-containing metal pigment according to claim 1.
21. A process for producing a pigmented coating agent, comprising
introducing the platelet-shaped copper-containing metal pigment
according to claim 1 into a coating agent
22. A process for producing a pigmented coating agent, according to
claim 21, wherein the pigmented coating agent is a powder
coating.
23. A process for producing a pigmented coating agent, according to
claim 21, wherein the pigmented coating agent is a varnish for use
in a coil-coating method.
24. A cosmetic product selected from the group consisting of body
powder, face powder, pressed powder, loose powder, face makeup,
powder cream, cream makeup, emulsion makeup, wax makeup,
foundation, mousse makeup, blusher, eye makeup, eyeshadow, mascara,
eyeliner, liquid eyeliner, eyebrow pencil, lip balm, lipstick, lip
gloss, lip liner, hair styling compositions, hair spray, hair
mousse, hair gel, hair wax, hair mascara, permanent hair dyes,
semi-permanent hair dyes, temporary hair dyes, skin care
compositions, lotions, gels, emulsions and nail polish
compositions, the cosmetic product comprising at least one
platelet-shaped copper-containing metal pigment according to claim
1.
25. The cosmetic product according to claim 24, wherein the
cosmetic product is a nail polish composition.
26. A method for producing a platelet-shaped copper-containing
metal pigment according to claim 1, comprising: (1a) coating
platelet-shaped copper-containing metal pigment with metal oxide,
(1b) coating the platelet-shaped copper-containing metal pigment
coated with metal oxide obtained in step (1a) with the educt(s) of
a chemically non-reactive plastic layer, (1c) curing or
polymerizing the copper-containing metal pigment pigments coated
with the educt(s) of the chemically non-reactive plastic layer in
step (1b), or (2a) coating platelet-shaped copper-containing metal
pigment pigments with the educt(s) of the a chemically non-reactive
plastic layer, (2b) curing or polymerizing the platelet-shaped
copper-containing metal pigment pigments coated with the educt(s)
of the chemically non-reactive plastic layer in step (2a), (2c)
coating the platelet-shaped copper-containing metal pigment
pigments coated with chemically non-reactive plastic layer obtained
in step (2b) with metal oxide.
27. The method for producing a platelet-shaped copper-containing
metal pigment according to claim 26, wherein the educt or the
educts of the chemically non-reactive plastic layer are monomers
selected from the group consisting of vinyl-functional monomers,
(meth)acrylate-functional monomers, and mixtures thereof and in
that the curing or polymerization of the monomers takes place
thermally during the production of the chemically non-reactive
plastic layer.
28. The method for producing a platelet-shaped copper-containing
metal pigment according to claim 26, wherein the curing or
polymerization in step 1(c) or step 2(b) takes place by radical
polymerization using polymerization initiators.
29. The platelet-shaped copper-containing metal pigment according
to claim 1, wherein the plastic layer is prepared from at least one
monomer selected from the group consisting of isoamyl acrylate,
lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, ethoxy
diethylene glycol acrylate, methoxy triethylene glycol acrylate,
methoxy polyethylene glycol acrylate, methoxy dipropylene glycol
acrylate, phenoxyethyl acrylate, phenoxy polyethylene glycol
acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate,
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic
acid, 2-acryloyloxyethyl phthalic acid,
2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, triethylene glycol
diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate,
1,9-nonanediol diacrylate, dimethylol tricyclodecane diacrylate,
trimethylolpropane triacrylate, pentaerythritol triacrylate,
pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate,
2-hydroxy-3-acryloyloxy propyl methacrylate, isooctyl acrylate,
isomyristyl acrylate, isostearyl acrylate, 2-ethyl hexyl diglycol
acrylate, 2-hydroxybutyl acrylate, 2-acryloyloxyethyl
hexahydrophthalic acid, hydroxy pivalic acid neopentyl glycol
diacrylate, polytetraethylene glycol diacrylate,
ditrimethylolpropane tetraacrylate, methyl methacrylate, ethyl
methacrylate, n-butyl methacrylate, isobutyl methacrylate,
2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl
methacrylate, tridecyl methacrylate, n-stearyl methacrylate,
methoxydiethylene glycol methacrylate, methoxy polyethylene glycol
methacrylate, cyclohexyl methacrylate, tetrahydrofurfural
methacrylate, benzyl methacrylate, phenoxyethyl methacrylate,
isobornyl methacrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate,
2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl
hexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl
phthalate, ethylene glycol dimethacrylate, diethylene glycol
dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol
dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol
dimethacrylate, trimethylolpropane trimethacrylate, glycerol
dimethacrylate, 2-hydroxy-3-acryloyloxy propyl methacrylate,
t-butyl methacrylate, isostearyl methacrylate, methoxytriethylene
glycol methacrylate, n-butoxyethyl methacrylate,
3-chloro-2-hydroxypropyl methacrylate, triethylene glycol
dimethacrylate, neopentyl glycol dimethacrylate, acrylic acid,
methacrylic acid, and mixtures thereof.
30. The platelet-shaped copper-containing metal pigment according
to claim 1, wherein the plastic layer is prepared from at least one
monomer selected from the group consisting of 1,6-hexanediol
diacrylate, 1,9-nonanediol diacrylate, dimethylol tricyclodecane
diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane
triacrylate, trimethylolpropane trimethacrylate and mixtures
thereof.
31. The platelet-shaped copper-containing metal pigment according
to claim 29, wherein the at least one plastic layer is prepared
from at least one monomer and at least one adhesion promoter
selected from the group consisting of organofunctional silanes,
titanates, aluminates, phosphonic acids, phosphoric acid esters,
zirconates and mixtures thereof.
32. The platelet-shaped copper-containing metal pigment according
to claim 1, further comprising at least one layer prepared from at
least one adhesion promoter selected from the group consisting of
organofunctional silanes, titanates, aluminates, phosphonic acids,
phosphoric acid esters, zirconates and mixtures thereof, the layer
being positioned between the at least one enveloping metal oxide
layer and the at least one enveloping chemically non-reactive
plastic layer.
Description
[0001] The invention relates to copper-containing metal pigments
with at least one enveloping metal oxide layer and at least one
enveloping plastic layer, as well as a method for the production
thereof. The invention furthermore relates to a coating agent, as
well as a coated object.
[0002] Copper-containing metal pigments, in particular metallic
effect pigments, such as copper pigments or brass pigments, which
are also called gold bronze pigments, are often used in the
graphics industry, for example in printer inks.
[0003] Copper-containing metal pigments are problematic to use
because of their copper content. Copper-containing pigments, for
example copper-containing metallic effect pigments, readily release
Cu(I) ions to the surroundings, for example a varnish or a paint.
The Cu(I) ions readily change into Cu(II) under the influence of
moisture. The change in the oxidation state from Cu(I) to Cu(II) is
necessarily accompanied by a reduction of components of the
surroundings, for example of binder components of a varnish or a
paint.
[0004] In addition, in particular Cu(II) ions form colored
complexes which can have a disruptive effect on the hue of the
corresponding application. For example, Cu(II) ions form intensely
blue copper complexes under alkaline conditions, in particular in
the presence of amines.
[0005] Above all, however, the Cu(II) ions, and in the case of gold
bronze pigments also of Zn(II) ions, can bring about a gelling of
the binder, which makes the corresponding application unusable.
[0006] For this reason, for example copper or gold bronze pigments
which are coated with SiO.sub.2 according to IDE 102 38 090 A1
cannot be reliably used in nail polishes.
[0007] The above-named effects are associated specifically with
copper-containing metal pigments, and therefore have no counterpart
in other metal pigments, for example in metal pigments consisting
of aluminum, iron, tin, etc.
[0008] According to the teaching of WO 2009/149834 A2,
copper-containing metallic effect pigments as well as coating
agents with copper-containing metallic effect pigments are provided
in which the above-named copper-specific problems are solved in
that a cellulose derivative, selected from the group consisting of
alkyl cellulose, hydroxyalkyl cellulose, alkyl(hydroxyalkyl)
cellulose and mixtures thereof, is present as a further
component.
[0009] These special cellulose derivatives can theoretically be
added to liquid coating agents such as printer inks, varnishes or
paints. However, for example incompatibilities often prevent the
use of such cellulose derivatives.
[0010] WO 2007/017195 A2 discloses in general metallic effect
pigments with a coating. The coating is characterized in that it
comprises a mixed inorganic/organic layer. The mixed layer contains
an inorganic network and at least one organic component, wherein
the organic component is an organic oligomer and/or polymer which
is at least partially covalently bonded to the inorganic network
via one or more organic network formers.
[0011] It has been shown that the production of mixed
inorganic/organic layers is expensive in terms of process
technology.
[0012] Metallic effect pigments with a coating are also known in
general from WO 2005/063897 A2. These metallic effect pigments are
coated with oligomeric and/or polymeric binders that can be
chemically cross-linked and/or can be cross-linked under the action
of heat, IR radiation, UV radiation and/or electron beams. This
still chemically reactive binder coating allows a reaction with the
binder of a varnish or a printer ink after application of the metal
pigment. A pre-coating with SiO.sub.2 can be arranged under the
binder coating.
[0013] It has been shown that, in the case of copper-containing
metal pigments with the coating known from WO 2005/063897 with a
not yet cross-linked binder coating, the release of copper ions to
the surroundings is not reliably prevented. In addition, relatively
large quantities of binder have to be used for the coating, which
leads e.g. to a reduced covering capacity.
[0014] DE 198 20 112 A1 discloses effect pigments coated with
reactive orientation additives. The subject of this application
essentially consists of aluminum effect pigments which can be
coated with a coating of metal oxides or polymers. Orientation
additives which enable a covalent bonding to the binder of a paint
or a varnish are then arranged on this coating.
[0015] Finally, metallic effect pigments coated with synthetic
resin, in particular aluminum effect pigments, are known from DE 40
30 727 A1.
[0016] A double coating of SiO.sub.2 and a synthetic resin of
metallic effect pigments is known from US 2009/0117281 A1. This
coating makes it possible to use the metal pigments in aqueous
formulations and brings about an improved chemicals stability and
water resistance of the films to which it has been applied. US
2009/0117281 A1 is clearly aimed at the use of aluminum effect
pigments.
[0017] Metallic effect pigments with improved chemicals stability
are also described in WO 2008/095697 A1.
[0018] With the exception of WO 2009/149834 A2 and WO 2008/095697
A1, the above-listed state of the art relates fundamentally to the
coating of aluminum effect pigments, in order to provide
corrosion-stable aluminum effect pigments.
[0019] Apart from WO 2009/149834 A2, none of the above-named
documents from the state of the art addresses the problem that
copper-containing pigments release copper ions, which can then lead
to undesired effects, to the surroundings.
[0020] The object of the present invention is therefore to provide
copper-containing metal pigments, in particular metallic effect
pigments, which are stabilized such that no disadvantageous
quantities of copper ions are released to the surroundings. For
example, such disadvantageous quantities of copper ions discolor
nail polish green, allow it to gel or make redispersal by means of
shaking impossible.
[0021] Furthermore the copper-containing metal pigments according
to the invention are to sustain as little damage as possible,
preferably none, to other application-specific properties such as
for example covering capacity, color, etc. e.g. during the process
of baking a powder coating or a coil coating.
[0022] Furthermore, a further object is to provide coating agents
which contain the copper-containing metal pigments according to the
invention and sustain as little as possible, preferably none, of
the above-named damage to application-specific properties.
[0023] In addition, the object of the present invention is to
provide a coated object which contains or has the platelet-shaped
copper-containing metal pigments according to the invention or
which contains or has the above-named coating agent according to
the invention and sustains as little as possible, preferably none,
of the above-named damage to application-specific properties.
[0024] A further object of the invention is to provide
copper-containing metal pigments, in particular metallic effect
pigments, which can be produced in a simple manner in terms of
process technology.
[0025] The object on which the invention is based is achieved by
providing platelet-shaped copper-containing metal pigments, wherein
the platelet-shaped copper-containing pigments have an elemental
copper content of at least 50 wt.-%, relative to the weight of the
uncoated copper-containing metal pigment, and wherein the
copper-containing metal pigments have at least one enveloping metal
oxide layer and at least one enveloping chemically non-reactive
plastic layer, and the sum of the amount of the at least one
chemically non-reactive plastic layer and the amount of the at
least one chemically non-reactive metal oxide layer lies in a range
of from 10 to 50 wt.-%, relative to the weight of the uncoated
metal pigment, and the weight ratio of the at least one metal oxide
layer to the at least one chemically non-reactive plastic layer
lies in a range of from 1:2 to 1:20.
[0026] Preferred developments of the platelet-shaped
copper-containing metal pigments according to the invention are
given in dependent claims 2 to 18.
[0027] Furthermore, the object on which the invention is based is
achieved by a coating agent which contains the platelet-shaped
copper-containing metal pigments according to the invention.
[0028] In addition, the object on which the invention is based is
achieved by a coated object which contains or has the
platelet-shaped copper-containing metal pigments according to the
invention or which contains or has the above-named coating agent
according to the invention.
[0029] The object on which the invention is based is also achieved
by the use of the platelet-shaped copper-containing metal pigments
according to the invention in a coating agent.
[0030] The object on which the invention is based is furthermore
achieved by providing a method for producing one of the
platelet-shaped copper-containing metal pigments according to the
invention which comprises the following steps:
[0031] (1a) coating platelet-shaped copper-containing metal
pigments with metal oxide,
[0032] (1b) coating the platelet-shaped copper-containing metal
pigments coated with metal oxide obtained in step (1a) with the
educt(s) of the chemically non-reactive plastic layer,
[0033] (1c) curing or polymerizing the copper-containing metal
pigments coated with the educt(s) of the chemically non-reactive
plastic layer in step (1b), or
[0034] (2a) coating the platelet-shaped copper-containing metal
pigments with the educt(s) of the chemically non-reactive plastic
layer,
[0035] (2b) curing or polymerizing the platelet-shaped
copper-containing metal pigments coated with the educt(s) of the
chemically non-reactive plastic layer in step (2a),
[0036] (2c) coating the platelet-shaped copper-containing metal
pigments coated chemically non-reactive plastic layer obtained in
step (2b) with metal oxide.
[0037] The sum of the amount of the at least one chemically
non-reactive plastic layer and the amount of the at least one
chemically non-reactive metal oxide layer necessarily lies in a
range of from 10 to 50 wt.-%, relative to the weight of the
uncoated metal pigment. Within this range, the weight ratio of the
at least one metal oxide layer to the at least one chemically
non-reactive plastic layer lies in a range of from 1:2 to 1:20. In
this respect, weight ratios which lie within the range of from 1:2
to 1:20, but outside the range of from 10 to 50 wt.-% are not
embodiments according to the invention.
Platelet-Shaped Copper-Containing Metal Pigments
[0038] The platelet-shaped copper-containing metal pigments
according to the invention have an elemental copper content of at
least 50 wt.-%, preferably of at least 60 wt.-%, further preferably
of at least 70 wt.-%, still further preferably of at least 80
wt.-%, still further preferably of at least 90 wt.-%, in each case
relative to the weight of the uncoated copper-containing metal
pigment. Within the meaning of the invention, by the above-named
elemental copper content is also meant the proportion of copper
contained in an alloy.
[0039] According to an embodiment of the invention, the
platelet-shaped copper pigments, also called copper effect
pigments, preferably have a copper content of from 98 to 100 wt.-%,
preferably from 99 to 99.999 wt.-%, in each case relative to the
weight of the uncoated copper-containing metal pigments. It goes
without saying that a person skilled in the art also reads the
detail 100 wt.-% copper to include usual foreign metals possibly
contained in trace amounts. The term "trace amounts" within the
meaning of the present invention denotes quantities of at most 0.01
wt.-%.
[0040] According to a further preferred embodiment, the
platelet-shaped copper-containing metal pigments are brass pigments
containing zinc and copper which are also called gold bronzes.
[0041] In further preferred embodiments, the platelet-shaped
copper-containing metal pigments are oxidized copper pigments or
oxidized brass pigments. Such effect pigments are obtained by
so-called "fire bronzing". The metallic effect pigments are
oxidized here in a targeted manner under the action of heat. The
metal oxide film that forms leads to interference effects as well
as, through the reddish intrinsic color of copper oxide, to a
correspondingly modified body color.
[0042] Brass effect pigments, usually called "gold bronze",
preferably have a copper content of from 70 to less than 98 wt.-%,
preferably 75 to 90 wt.-%, in each case relative to the weight of
the uncoated copper-containing metal pigments. The zinc content
accordingly preferably lies between 30 and more than 2 wt.-%,
preferably at 25 to 10 wt.-%, for example at 25 wt.-%, wherein
optionally up to 2 wt.-%, preferably less than 1 wt.-%, of the
copper can be replaced by contaminations by other metals, in each
case relative to the weight of the uncoated copper-containing metal
pigment.
[0043] In the case of brass effect pigments or gold bronze effect
pigments, the hue is determined by the copper-zinc ratio of the
alloy.
[0044] Gold bronze effect pigments are traded commercially in
characteristic natural hues, as "pale gold" with a copper
proportion of approx. 90% and a remainder of approx. 10 wt.-% zinc,
as "rich pale gold" with a copper proportion of approx. 85 wt.-%
and a remainder of approx. 15 wt.-% zinc and as "rich gold" with a
copper proportion of approx. 70 wt.-% and a remainder of approx. 30
wt.-% zinc. The detail in wt.-% relates in each case to the
uncoated copper-containing metal pigment.
[0045] In a preferred embodiment, the uncoated brass effect
pigments contain a "contamination" with for example 0.1 to 2 wt.-%,
preferably 0.5 to 1.8 wt.-%, aluminum, in each case relative to the
weight of the uncoated copper-containing metallic effect pigment.
The alloys which have such a proportion of aluminum have proved to
be more corrosion-stable than brass effect pigments containing
exclusively copper and zinc.
[0046] In particular preferred embodiments, the platelet-shaped
copper-containing uncoated metal pigments are selected from the
group consisting of copper pigments, brass pigments, oxidized
copper pigments, oxidized brass pigments and mixtures thereof.
[0047] Incident light is reflected, as if directed by a mirror, at
the surfaces of the platelet shape of these metallic effect
pigments, whereby the metallic effect, in the present case the
effect of copper-containing metallic effect pigments, is brought
about for an observer.
[0048] The platelet-shaped copper-containing uncoated metal
pigments which are used according to the present invention have an
average pigment diameter (D.sub.50) from a range of from about 1
.mu.m to about 200 .mu.m, preferably from about 3 .mu.m to 120
.mu.m, still further preferably from about 5 .mu.m to about 80
.mu.m. Pigment diameters from a range of from about 10 .mu.m to
about 50 .mu.m, preferably from about 15 .mu.m to about 40 .mu.m,
have also proved to be very suitable.
[0049] The size distribution of the particles is preferably
determined by means of laser granulometry. In this method, the
particles can be measured in the form of a powder. The scattering
of the irradiated laser light is detected in different spatial
directions and evaluated according to the Fraunhofer diffraction
theory. The particles are treated computationally as spheres. Thus,
the determined diameters always relate to the equivalent spherical
diameter determined over all spatial directions, irrespective of
the actual shape of the particles. The evaluation of the
diffraction data is the basis for a model which is aimed at the
diameter of an equivalent sphere. Therefore, no absolute values are
obtained, but the measured diameters have become accepted as
reliable relative values in the description of the size
characteristics of platelet-shaped metal pigments. The size
distribution is determined, calculated in the form of a volume
average relative to the equivalent spherical diameter. This
volume-averaged size distribution can be represented as a total
frequency distribution. The total frequency distribution is
characterized in a simplified manner by different characteristic
values, for example the D.sub.50 value. The term "average pigment
diameter" or "D.sub.50" within the meaning of the present invention
denotes the particle size at which 50% of the above-named
particle-size distribution volume-averaged by means of laser
granulometry lies below and 50% of the above-named particle-size
distribution volume-averaged by means of laser granulometry lies
above the given value. The measurements can be carried out for
example with the particle-size analyzer HELOS from Sympatec GmbH,
Clausthal-Zellerfeld, Germany.
[0050] The average thickness (h.sub.50) of the copper-containing
uncoated metallic effect pigments used in the present invention
preferably lies in a range of from 25 nm to about 2 .mu.m,
preferably from about 40 nm to about 1.5 .mu.m, still further
preferably from about 70 nm to 1.1 .mu.m, still further preferably
from about 80 nm to about .mu.m. The term "average thickness" or
"h.sub.50" within the meaning of the invention relates to the
arithmetic average of the thicknesses of at least 100 metallic
effect pigments by means of scanning electron microscopy (SEM).
Attention is to be paid here to as good as possible an orientation
of the platelets in the application medium. For this, the metallic
effect pigments can be pre-treated beforehand by suitable
additives. Then the cured varnish is sanded and observed in SEM
after usual sample preparation of the cross-ground section. For the
counting, only particles which have a good orientation are
selected. The average thickness or the h.sub.50 value relates to
the uncoated copper-containing metal pigment or metallic effect
pigment.
[0051] An average thickness (h.sub.50) of from about 90 nm to about
600 nm, further preferably from about 110 nm to about 450 nm, has
also proved to be very suitable.
[0052] The size-thickness ratio, which is also called the aspect
ratio, preferably lies in a range of from about 1000:1 to 3:1,
further preferably from about 700:1 to about 10:1, still further
preferably to about 500:1 to 20:1. The term "size-thickness ratio"
or "aspect ratio" within the meaning of the invention relates to
the ratio of D.sub.50 to h.sub.50.
[0053] In particular embodiments, furthermore a size-thickness
ratio of from about 450:1 to 10:1, still further preferably from
about 400:1 to 15:1, has proved to be advantageous. Furthermore, it
has been found in particular variants of the invention that a very
suitable size-thickness ratio lies in the range of from about 80:1
to 3:1, further preferably from about 50:1 to 5:1, still further
preferably from about 40:1 to 10:1.
[0054] The inventors have surprisingly discovered that an effective
encapsulation of copper-containing metal pigments can be achieved
if at least one enveloping metal oxide layer and at least one
enveloping chemically non-reactive plastic layer are applied to the
copper-containing pigments.
[0055] In specific particularly preferred embodiments, the at least
one enveloping metal oxide layer is arranged between
platelet-shaped copper-containing metal pigment and the at least
one enveloping chemically non-reactive plastic layer. Such a layer
structure has been shown to be particularly effective in respect of
for example the chemicals stability and in particular the
prevention of the discharge of copper ions.
[0056] In still other embodiments, on the other hand, it is
preferred that the at least one chemically non-reactive plastic
layer is arranged between the copper-containing metal pigment and
the at least one enveloping metal oxide layer. Metal pigments with
such a layer structure are characterized for example by a
particular hardness.
[0057] It has moreover surprisingly been shown that metal pigments
with an at least two-layered coating structure with at least one
enveloping metal oxide layer and at least one enveloping chemically
non-reactive plastic layer are characterized by a particular
stability also vis-a-vis mechanical influences, for example
abrasive influences.
[0058] Without being understood as limiting the present invention,
it is assumed that the mechanical stability for example of the
copper-containing metal pigments according to the invention with an
external chemically non-reactive plastic layer is to be attributed
to the fact that the above-named chemically non-reactive plastic
layer has a degree of elasticity, i.e. is not brittle. Thus,
mechanical forces which act on the copper-containing metal pigments
according to the invention can be absorbed by the outer enveloping
chemically non-reactive plastic layer.
Chemically Non-Reactive Plastic Layer:
[0059] By a "chemically non-reactive plastic layer" is meant
according to the invention that the plastic layer is substantially
completely, preferably completely, cured. This cured plastic layer
therefore does not substantially react with the binder of a coating
agent, such as for example a varnish, for example a powder coating,
or a paint. According to a preferred variant, no reaction between
the cured plastic layer and the binder of a coating agent takes
place.
[0060] Thus, the "chemically non-reactive plastic layer" is
certainly not a coating of not yet cured binder, such as disclosed
in WO 2005/063897 A2. A binder is characterized in that it cures
only later in the application, for example as a resin/hardener
system or by radical polymerization.
[0061] In this case, however, the metal pigments are irreversibly
incorporated into the cured powder coating. Thus, the invention
makes it possible to provide a set of isolated copper-containing
metal pigments which have at least one enveloping metal oxide layer
and an enveloping chemically non-reactive plastic layer. In
particular, the present invention makes it possible to provide
powders and pastes containing the copper-containing metal pigments
according to the invention.
[0062] In the case of conventional metallic effect pigments,
protective layers are applied which are to protect the metallic
effect pigments, usually aluminum and/or iron effect pigments,
against corrosive influences from the surroundings.
[0063] In the present case, it has been shown that
copper-containing pigments can be effectively encapsulated, with
the result that no noticeable quantities of copper ions, preferably
no copper ions, are released by the copper-containing pigments into
the surroundings, for example a varnish, a paint, a plastic or a
cosmetic product.
[0064] The copper-containing metal pigments according to the
invention have an average thickness of the plastic layer in a range
of from 100 nm to 300 nm, preferably from 120 nm to 250 nm and
particularly preferably from 150 nm to 230 nm. Below an average
thickness of the plastic layer of 100 nm, a clear diminution of the
advantageous properties is observed. Above an average thickness of
300 nm in turn, the covering capacity and/or the luster of the
metal pigments according to the invention are adversely affected in
their applications.
[0065] It is assumed that these relatively thick plastic layers act
above all as a barrier layer vis-a-vis water and other corrosive
chemicals. Without being understood as limiting the present
invention, it is the view of the inventors, however, that the layer
also retains copper and/or zinc ions to a certain extent in the
coating, with the result that these ions cannot enter the
surrounding application medium.
[0066] In particular embodiments, it is preferred in particular
that the weight proportion of the at least one chemically
non-reactive plastic layer is at least 8 wt.-%, preferably at least
9 wt.-%, further preferably at least 9.5 wt.-%, more preferably at
least 10 wt.-% and still more preferably at least 11 wt.-%, in each
case relative to the weight of the uncoated copper-containing metal
pigment.
[0067] The weight proportion of the plastic layers, relative to the
weight of the uncoated copper-containing metal pigment,
substantially depends on the specific surface area of the uncoated
metal pigment. According to further preferred embodiments, it lies
in a range of from 8 to 40 wt.-%, preferably in the range of from 9
to 35 wt.-%, further preferably in the range of from 9.5 to 30
wt.-%, more preferably in the range of from 10 to 23 wt.-% and
still more preferably in the range of from 11 to 18 wt.-%, in each
case relative to the weight of the uncoated copper-containing metal
pigment.
[0068] According to further preferred embodiments, the at least one
plastic layer substantially consists of a plastic which is selected
from the group consisting of polyacrylate, polymethacrylate,
polyacrylamide, polyacrylonitrile, polyvinyl chloride, polyvinyl
acetate, polyamide, polyalkene, polydiene, polyalkyne, polyalkylene
glycol, epoxy resin, polyester, polyether, polyol, polyurethane,
polycarbonate, polyethylene terephthalate and mixtures thereof.
[0069] According to a preferred embodiment, the at least one
plastic layer substantially consists of a plastic which is selected
from the group consisting of polyacrylate, polymethacrylate,
polyurethane, polyester and mixtures thereof. Copper-containing
metallic effect pigments with at least one such plastic layer are
characterized for example by an increased UV-resistance. For
example, polyacrylates, polymethacrylates or mixtures thereof have
proved to be particularly suitable plastics for producing plastic
layers with increased UV-resistance. In particular embodiments of
the invention, the at least one plastic layer therefore
substantially consists of polyacrylates and/or
polymethacrylates.
[0070] For example, isoamyl acrylate, lauryl acrylate, stearyl
acrylate, butoxyethyl acrylate, ethoxy diethylene glycol acrylate,
methoxy triethylene glycol acrylate, methoxy polyethylene glycol
acrylate, methoxy dipropylene glycol acrylate, phenoxyethyl
acrylate, phenoxy polyethylene glycol acrylate, tetrahydrofurfuryl
acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate,
2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid,
2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, triethylene glycol
diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate,
1,9-nonanediol diacrylate, dimethylol tricyclodecane diacrylate,
trimethylolpropane triacrylate, pentaerythritol triacrylate,
pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate,
2-hydroxy-3-acryloyloxy propyl methacrylate, isooctyl acrylate,
isomyristyl acrylate, isostearyl acrylate, 2-ethyl hexyl diglycol
acrylate, 2-hydroxybutyl acrylate, 2-acryloyloxyethyl
hexahydrophthalic acid, hydroxy pivalic acid neopentyl glycol
diacrylate, polytetraethylene glycol diacrylate,
ditrimethylolpropane tetraacrylate, methyl methacrylate, ethyl
methacrylate, n-butyl methacrylate, isobutyl methacrylate,
2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl
methacrylate, tridecyl methacrylate, n-stearyl methacrylate,
methoxydiethylene glycol methacrylate, methoxy polyethylene glycol
methacrylate, cyclohexyl methacrylate, tetrahydrofurfural
methacrylate, benzyl methacrylate, phenoxyethyl methacrylate,
isobornyl methacrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate,
2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl
hexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl
phthalate, ethylene glycol dimethacrylate, diethylene glycol
dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol
dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol
dimethacrylate, trimethylolpropane trimethacrylate, glycerol
dimethacrylate, 2-hydroxy-3-acryloyloxy propyl methacrylate,
t-butyl methacrylate, isostearyl methacrylate, methoxytriethylene
glycol methacrylate, n-butoxyethyl methacrylate,
3-chloro-2-hydroxypropyl methacrylate, triethylene glycol
dimethacrylate, neopentyl glycol dimethacrylate or mixtures thereof
are used as monomers for producing polyacrylates and
polymethacrylates.
[0071] At least one monomer with at least two, particularly
preferably three, reactive double bonds (cross-linker) is
particularly preferably used.
[0072] The monomer therefore particularly preferably contains or
consists of 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate,
dimethylol tricyclodecane diacrylate neopentyl glycol
dimethacrylate trimethylolpropane triacrylate, trimethylolpropane
trimethacrylate or mixtures thereof.
[0073] Furthermore, the acrylate-/methacrylate-containing plastic
layer can additionally have acrylic acid and/or methacrylic acid as
well as further radically polymerizable unsaturated compounds.
[0074] An increased UV-stability is desired when the
copper-containing metal pigments according to the invention, in
particular copper-containing metallic effect pigments, are used in
external applications, such as for example in a car paint, a facade
paint, etc.
[0075] According to a further variant according to the invention,
the plastic layer is selected from the group consisting of
polyamide, polycarbonate, polyvinyl chloride, polyethylene
terephthalate and mixtures thereof. Copper-containing metal
pigments with at least one such plastic layer are characterized for
example by an increased temperature stability.
[0076] According to a preferred embodiment of the invention, the
plastic is temperature-stable up to a temperature of at least
180.degree. C., further preferably of at least 260.degree. C.,
still further preferably up to a temperature of at least
350.degree. C. By temperature-stable is meant that the plastic
coating of the platelet-shaped copper-containing metal pigments
does not melt and/or break down at the above-named temperature. A
possible melting and/or break-down at a given temperature can be
tested for example by means of dynamic differential
calorimetry.
[0077] According to a further preferred embodiment, physically
bonded surface modifiers are applied to the enveloping chemically
non-reactive plastic layer.
Metal Oxide Layer:
[0078] According to a preferred variant of the invention, the at
least one metal oxide layer is selected from the group consisting
of silicon oxide, aluminum oxide, boron oxide, zirconium oxide,
cerium oxide, iron oxide, titanium oxide, chromium oxide, tin
oxide, molybdenum oxide, oxide hydrates thereof, hydroxides thereof
and mixtures thereof. In particular preferred embodiments, the at
least one metal oxide layer is characterized in that the at least
one metal oxide layer substantially consists of silicon oxide.
[0079] Within the framework of this invention, by the term
"substantially consisting of silicon oxide" is meant that the layer
consists predominantly of silicon oxide, preferably SiO.sub.2, but
can also contain up to 20 wt.-% water, relative to the silicon
oxide layer. Furthermore, in a sol-gel synthesis from
tetraalkoxysilanes, the silicon oxide can contain up to 5 wt.-%
alkoxy groups which have not been hydrolyzed and condensed.
[0080] At least one, preferably all, of the at least one enveloping
metal oxide layers preferably consists/consist of a silicon oxide
layer or silicon oxide layers, preferably an SiO.sub.2 layer or
SiO.sub.2 layers, and/or aluminum oxide layer or aluminum oxide
layers, preferably an Al.sub.2O.sub.3 layer or Al.sub.2O.sub.3
layers. In particular preferred embodiments, at least one,
preferably all, of the at least one enveloping metal oxide layers
consists/consist of a silicon oxide layer(s), preferably an
SiO.sub.2 layer. In further particular preferred embodiments, at
least one, preferably all, of the at least one enveloping metal
oxide layers consists or consist of an aluminum oxide layer or
aluminum oxide layers, preferably an Al.sub.2O.sub.3 layer or
Al.sub.2O.sub.3 layers. In specific particularly preferred
embodiments, the at least one enveloping metal oxide layer is one
(1) silicon oxide layer, preferably one (1) SiO.sub.2 layer.
[0081] It has surprisingly been shown that the use of a particular
minimum quantity of metal oxide layer is advantageous in order to
achieve for example a particularly high oxidation stability. In
particular embodiments, it is therefore preferred that the weight
proportion of the at least one metal oxide layer is at least 0.9
wt.-%, preferably at least 1.0 wt.-%, more preferably at least 1.5
wt.-%, still more preferably at least 2.0 wt.-% and most preferably
at least 2.5 wt.-%, in each case relative to the weight of the
uncoated copper-containing metal pigment.
[0082] According to a further preferred embodiment of the
invention, the weight proportion of the metal oxide layer lies in a
range of from 0.9 to 12 wt.-%, further preferably from 1 to 10
wt.-%, and particularly preferably from 1.5 to 9 wt.-% and quite
particularly preferably from 2 to 8 wt.-%, in each case relative to
the weight of the uncoated copper-containing metal pigment.
[0083] In addition, it was surprisingly found that in the case of
platelet-shaped copper-containing metal pigments in which a metal
oxide layer according to the invention was applied as the top
layer, it is particularly advantageous to apply a larger quantity
of the metal oxide layer. In particular embodiments, therefore, it
is preferred that the weight proportion of the at least one metal
oxide layer in platelet-shaped copper-containing metal pigments in
which a metal oxide layer according to the invention was applied as
the top layer is at least 0.9 wt.-%, relative to the weight of the
uncoated copper-containing metal pigment. In particular
embodiments, it is preferred in particular that the weight
proportion of the at least one metal oxide layer in platelet-shaped
copper-containing metal pigments in which a metal oxide layer
according to the invention was applied as the top layer is at least
1.0 wt.-% and in platelet-shaped copper-containing metal pigments
in which a chemically non-reactive plastic layer according to the
invention was applied as the top layer is at least 0.9 wt.-%;
preferably in platelet-shaped copper-containing metal pigments in
which a metal oxide layer according to the invention was applied as
the top layer is at least 1.5 wt.-% and in platelet-shaped
copper-containing metal pigments in which a chemically non-reactive
plastic layer according to the invention was applied as the top
layer is at least 1.0 wt.-%; more preferably in platelet-shaped
copper-containing metal pigments in which a metal oxide layer
according to the invention was applied as the top layer is at least
2.0 wt.-% and in platelet-shaped copper-containing metal pigments
in which a chemically non-reactive plastic layer according to the
invention was applied as the top layer is at least 1.5 wt.-%; and
still more preferably in platelet-shaped copper-containing metal
pigments in which a metal oxide layer according to the invention
was applied as the top layer is at least 2.5 wt.-% and in
platelet-shaped copper-containing metal pigments in which a
chemically non-reactive plastic layer according to the invention
was applied as the top layer is at least 2.0 wt.-%, in each case
relative to the weight of the uncoated copper-containing metal
pigment. Without being understood as limiting the present
invention, it is the view of the inventors that a larger quantity
of metal oxide is necessary to form an external metal oxide layer
which is sufficiently resistant for example to mechanical
influences and provides the desired stabilization of the metal
pigment. In particular embodiments, it is preferred in particular
that the weight proportion of the at least one enveloping metal
oxide layer in platelet-shaped copper-containing metal pigments in
which a chemically non-reactive plastic layer forms the top layer
of the coating lies in a range of from 0.9 to 12 wt.-% and in
platelet-shaped copper-containing metal pigments in which a metal
oxide layer forms the top layer of the coating lies in a range of
from 1.0 to 10 wt.-%, preferably in platelet-shaped
copper-containing metal pigments in which a chemically non-reactive
plastic layer forms the top layer of the coating lies in a range of
from 1.0 to 10 wt.-% and in platelet-shaped copper-containing metal
pigments in which a metal oxide layer forms the top layer of the
coating lies in a range of from 1.5 to 9 wt.-%, more preferably in
platelet-shaped copper-containing metal pigments in which a
chemically non-reactive plastic layer forms the top layer of the
coating lies in a range of from 1.5 to 9 wt.-% and in
platelet-shaped copper-containing metal pigments in which a metal
oxide layer forms the top layer of the coating lies in a range of
from 2.0 to 8 wt.-% and still more preferably in platelet-shaped
copper-containing metal pigments in which a chemically non-reactive
plastic layer forms the top layer of the coating lies in a range of
from 2.0 to 8 wt.-% and in platelet-shaped copper-containing metal
pigments in which a metal oxide layer forms the top layer of the
coating lies in a range of from 2.5 to 7 wt.-%, in each case
relative to the weight of the uncoated copper-containing metal
pigment.
[0084] The average thickness of the metal oxide layer preferably
lies in a range of from 2 nm to 25 nm, further preferably from 3 nm
to 20 nm. An average thickness in a range of from 5 nm to 10 nm has
also proved to be very suitable.
[0085] Surprisingly, in the platelet-shaped copper-containing metal
pigment according to the invention, one (1) thin metal oxide layer
in conjunction with one (1) chemically non-reactive plastic layer
already suffices on the one hand to protect the copper-containing
metal pigments from environmental influences and on the other hand
to prevent copper ions from being released by the copper-containing
metal pigment into the surroundings, for example a varnish, a
paint, a cosmetic product, etc.
[0086] In a very preferred embodiment, the metal oxide layer is
applied directly to the metal substrate as a first layer. In
particular in this embodiment it is assumed that the metal oxide
layer as a start represents a relatively effective barrier against
copper and/or zinc ions being discharged. Those metal ions that
still overcome this barrier are obviously effectively trapped in
the plastic layer.
Synergistic Action of the Two Layers:
[0087] It is assumed that the enveloping metal oxide layer and the
enveloping chemically non-reactive plastic layer interact in a
synergistic manner.
[0088] Firstly, it is assumed that the enveloping chemically
non-reactive plastic layer, i.e. the substantially completely
polymerized, preferably polymerized, and/or cured plastic layer
forms a plastic matrix so dense that any copper ions getting
through the SiO.sub.2 layer are reliably incorporated by the dense
plastic layer.
[0089] Secondly, it is assumed that any corrosive substances
getting through the chemically non-reactive plastic layer from the
surroundings of the copper-containing metal pigment according to
the invention, such as e.g. H.sup.+ or OH.sup.- ions, are also
trapped between the metal oxide layer and plastic layer, with the
result that these corrosive substances come into contact with the
copper-containing metal pigments only slightly, preferably not at
all. Any copper ions nevertheless released by corrosive influences
are then, as already stated above, presumably trapped between the
metal oxide layer and the chemically non-reactive plastic layer and
therefore not released to the surroundings, for example a paint or
a varnish.
[0090] Thus, the at least two-layered coating structure interacts
synergistically with an enveloping metal oxide layer and an
enveloping chemically non-reactive plastic layer, with the result
that any corrosive influences from the surroundings, for example
when the copper-containing pigments are used in a car paint, a
facade paint, etc., do not come into contact with copper and,
should this have happened, any copper ions released do not enter
the surroundings.
[0091] A further important aspect is the oxidation of the
platelet-shaped copper-containing metal pigments with atmospheric
oxygen at temperatures above approx. 80.degree. C. This occurs for
example both during the curing of powder coating (baking
temperatures approx. 200.degree. C.) or during coil-coating
varnishing (baking temperatures approx. 280.degree. C.). Here, it
has surprisingly been shown that a thin metal oxide layer combined
with the chemically non-reactive plastic layer already suffices to
prevent an oxidation of the copper-containing metal pigment.
Although the plastic layer is oxygen-permeable, it gives the
product the necessary chemicals stability.
[0092] In particular embodiments, it is preferred in particular
that the sum of the amount of the polymer layer and the amount of
the metal oxide layer lies in a range of from 13 to 40 wt.-%,
preferably in a range of from 14 to 35 wt.-%, more preferably in a
range of from 15 to 33 wt.-%, still more preferably in a range of
from 16 to 29 wt.-%, in each case relative to the weight of the
uncoated metal pigment.
[0093] It is preferred according to the invention to keep the sum
of the amount of the polymer layer and the amount of the metal
oxide layer as low as possible overall.
[0094] In this way, an optimum covering capacity of the metallic
effect pigments is guaranteed. In addition it has been shown that,
if the layers are too thick, the metallic effect pigments can tend
to agglomerate. Furthermore, in the case of thicker layers which
are above 50 wt.-%, relative to the weight of the uncoated metal
pigment, the protective action surprisingly decreases. It is
assumed that thicker layers have a low quality with respect to
their protective properties, because they are more brittle.
[0095] It is essential to the invention that the chemically
non-reactive plastic layer is applied in a much higher proportion
by weight relative to the metal oxide layer.
[0096] Particularly preferred embodiments have a weight ratio of
the at least one metal oxide layer to the at least one chemically
non-reactive plastic layer in a range of from 1:2.2 to 1:17,
preferably in a range of from 1:2.5 to 1:15, further preferably in
a range of from 1:2.7 to 1:13 and still further preferably in a
range of from 1:3 to 1:10.
[0097] Furthermore, it has surprisingly been shown that it is
advantageous in particular variants to choose a more narrow range
of the weight ratio of the at least one metal oxide layer to the at
least one chemically non-reactive plastic layer in platelet-shaped
copper-containing metal pigments in which a chemically non-reactive
plastic layer according to the invention was applied as the first
layer. In particular embodiments, it is therefore preferred that
the weight ratio of the at least one metal oxide layer to the at
least one chemically non-reactive plastic layer in platelet-shaped
copper-containing metal pigments in which a chemically non-reactive
plastic layer according to the invention was applied as the first
layer lies in a range of from 1:2.2 to 1:17 and in platelet-shaped
copper-containing metal pigments in which a metal oxide layer
according to the invention was applied as the first layer lies in a
range of from 1:2.0 to 1:20; preferably in platelet-shaped
copper-containing metal pigments in which a chemically non-reactive
plastic layer according to the invention was applied as the first
layer lies in a range of from 1:2.5 to 1:15 and in platelet-shaped
copper-containing metal pigments in which a metal oxide layer
according to the invention was applied as the first layer lies in a
range of from 1:2.2 to 1:17; further preferably in platelet-shaped
copper-containing metal pigments in which a chemically non-reactive
plastic layer according to the invention was applied as the first
layer lies in a range of from 1:2.7 to 1:13 and in platelet-shaped
copper-containing metal pigments in which a metal oxide layer
according to the invention was applied as the first layer lies in a
range of from 1:2.5 to 1:15; and still further preferably in
platelet-shaped copper-containing metal pigments in which a
chemically non-reactive plastic layer according to the invention
was applied as the first layer lies in a range of from 1:3 to 1:10
and in platelet-shaped copper-containing metal pigments in which a
metal oxide layer according to the invention was applied as the
first layer lies in a range of from 1:2.7 to 1:13. Without being
understood as limiting the invention, it is the view of the
inventors that a chemically non-reactive plastic layer applied
first of all provides a more irregular surface for subsequent
coatings, with the result that the use of a more precisely
specified weight ratio of the at least one metal oxide layer to the
at least one chemically non-reactive plastic layer in
platelet-shaped copper-containing metal pigments in which a
chemically non-reactive plastic layer according to the invention
was applied as the first layer proves to be advantageous in order
to bring about the effects according to the invention in a
particularly pronounced form.
[0098] In particular variants of the invention, ranges are
preferred in particular which are characterized by a quantity of
plastic of from 8 wt.-% to 40 wt.-% and a quantity of metal oxide
of from 0.9 wt.-% to 12 wt.-%, preferably a quantity of plastic of
from 9 wt.-% to 35 wt.-% and a quantity of metal oxide of from 1
wt.-% to 10 wt.-%, further preferably a quantity of plastic of from
10 wt.-% to 30 wt.-% and a quantity of metal oxide of from 1.5
wt.-% to 9 wt.-%, still further preferably a quantity of plastic of
from 12 wt.-% to 25 wt.-% and a quantity of metal oxide of from 2
wt.-% to 8 wt.-%, in each case relative to the weight of the
uncoated copper-containing metal pigment.
[0099] In specifically preferred embodiments, the at least one
chemically non-reactive plastic layer substantially consists of
polyacrylate and/or polymethacrylate and the at least one metal
oxide layer substantially consists of silicon oxide, preferably
SiO.sub.2, wherein the weight ratio of the at least one metal oxide
layer to the at least one chemically non-reactive plastic layer
lies in a range of from 1:2.2 to 1:17 and the sum of the amount of
the at least one chemically non-reactive plastic layer and the
amount of the at least one metal oxide layer lies in a range of
from 10 to 50 wt.-%, relative to the weight of the uncoated metal
pigment.
[0100] In further specific preferred embodiments, the at least one
chemically non-reactive plastic layer substantially consists of
polyacrylate and/or polymethacrylate and the at least one metal
oxide layer substantially consists of silicon oxide, preferably
SiO.sub.2, wherein the weight ratio of the at least one metal oxide
layer to the at least one chemically non-reactive plastic layer
lies in a range of from 1:2.5 to 1:15 and the sum of the amount of
the at least one chemically non-reactive plastic layer and the
amount of the at least one metal oxide layer lies in a range of
from 13 to 40 wt.-%, relative to the weight of the uncoated metal
pigment.
[0101] In further specific preferred embodiments, the at least one
chemically non-reactive plastic layer substantially consists of
polyacrylate and/or polymethacrylate and the at least one metal
oxide layer substantially consists of silicon oxide, preferably
SiO.sub.2, wherein the weight ratio of the at least one metal oxide
layer to the at least one chemically non-reactive plastic layer
lies in a range of from 1:2.2 to 1:17 and the sum of the amount of
the chemically non-reactive plastic layer and the amount of the
metal oxide layer lies in a range of from 13 to 40 wt.-%, relative
to the weight of the uncoated metal pigment. In particular ones of
the above-named specific preferred embodiments, the weight ratio of
the at least one metal oxide layer to the at least one plastic
layer lies in a range of from 1:2.5 to 1:15.
[0102] In further specific preferred embodiments, the weight ratio
of the at least one metal oxide layer to the at least one
chemically non-reactive plastic layer lies in a range of from 1:2.5
to 1:15.
[0103] In further preferred embodiments, the above-named specific
preferred embodiments are supplemented by the fact that the
proportion by weight of the silicon oxide, preferably SiO.sub.2,
layer lies in a range of from 1.5 to 9 wt.-%, relative to the
weight of the uncoated copper-containing metal pigment.
[0104] In further preferred embodiments, the above-named specific
preferred embodiments are supplemented by the fact that the
proportion by weight of the at least one chemically non-reactive
plastic layer lies in a range of from 10 to 35 wt.-%, relative to
the weight of the uncoated copper-containing metal pigment.
[0105] Optionally, one or more organofunctional silanes which
contain at least one radically polymerizable double bond,
preferably at least one acrylate and/or methacrylate group, can be
applied between the SiO.sub.2 layer and the plastic layer.
[0106] The copper-containing metal pigments according to the
invention have two important advantages as a result of the
relatively low thicknesses of the metal oxide layer and the
relatively high plastic layer thickness.
[0107] Firstly, the covering capacity, i.e. the surface area
covered per weight unit of pigment according to the invention, is
still very good, compared with the covering of an uncoated metal
pigment. The thicker the applied transparent coating is, the worse
the covering capacity becomes, because ever fewer metal particles
are present per gram of pigment. The covering capacity can
additionally be made worse if more fines of the metal pigments are
incorporated into the coating of larger pigments as the coating
thickness increases. However, these fines are critical for a good
covering capacity.
[0108] In this respect, it is advantageous if the coating has as
small a layer thickness as possible, because then fewer fines are
incorporated into the coating of larger pigments and these can thus
still contribute to the covering through a statistical distribution
in the varnish. In order to be able to keep the average layer
thickness of the coating low, it is a prerequisite that the applied
enveloping transparent coating effectively protects the
copper-containing metal pigment from corrosive environmental
influences and also prevents copper ions from being released into
the surroundings.
[0109] A combination of a thin metal oxide layer with a chemically
non-reactive plastic layer surprisingly makes it possible both to
protect the copper-containing metal pigment from corrosive
environmental influences and to effectively encapsulate the copper
ions so that they are not released into the surroundings. With
regard to the transparent coating with low layer thickness, the
copper-containing metal pigments according to the invention
therefore have an excellent covering capacity.
[0110] In particular embodiments, the at least one plastic layer is
obtained by means of an initiator-induced radical polymerization.
It has surprisingly been shown that, in the case of a radical
polymerization started by an initiator, a coarse chemically
non-reactive plastic layer is obtained. This is very advantageous
if the platelet-shaped copper-containing metal pigments according
to the invention are used in a powder coating. The behavior is
obviously such that a coarser surface structure of the chemically
non-reactive plastic layer effects an easier electrostatic
chargeability of the platelet-shaped copper-containing metal
pigments according to the invention. In the case of a stronger
electrostatic charge, the platelet-shaped copper-containing metal
pigments according to the invention can be applied more easily to a
workpiece to be varnished.
[0111] This leads, on the one hand, to a more effective varnishing
in which the proportion of powder coating not applied, the
so-called overspray, is reduced. On the other hand, workpieces to
be varnished can be provided with a higher-quality powder coating
varnishing within a shorter time.
[0112] In contrast to uses of the metallic effect pigments
according to the invention in powder coating, it has been shown
that smooth surfaces, such as form in the case of thermal
polymerization, are advantageous for wet coating uses such as coil
coating. Due to the smooth surfaces, there is a uniform passage of
the light through the varnish-coating boundary layer of the
pigment. Undesired scattering effects are thereby minimized, with
the result that these pigments appear more brilliant than
comparable metallic effect pigments from the state of the art. A
further advantage is that, due to the smaller surface, less binder
is needed to wet the pigments, with the result that higher pigment
loads are possible.
Further Layers:
[0113] One or more further layers can be arranged between the at
least one enveloping metal oxide layer and the at least one
enveloping chemically non-reactive plastic layer. These one or more
additional layers can also be for example additional metal oxide
layers. In particular embodiments, however, it is preferred that
the possibly present layers between the at least one enveloping
metal oxide layer and the at least one enveloping chemically
non-reactive plastic layer do not represent a metal oxide layer or
plastic layer within the meaning of the present invention.
[0114] In a preferred embodiment, however, organofunctional
silanes, titanates, aluminates, phosphonic acids (e.g. VPS: vinyl
phosphonic acid), phosphoric acid esters and/or zirconates are used
here as adhesion promoter and/or further layer component, wherein
organofunctional silanes are particularly preferred. These
compounds can bind for example particularly well to the metal
surface or metal oxide surface because of their known hydrolysis
and condensation reactions. The compounds should have at least one
chemically polymerizable group which is preferably adapted to the
plastic layer.
[0115] If the plastic layer consists for example of polyacrylates
and/or polymethacrylates, the organofunctional silane preferably
has at least one functional group which can be chemically reacted
with an acrylate group and/or methacrylate group of polyacrylate
and/or polymethacrylate. Radically polymerizable organic functional
groups have proved to be very suitable. Preferably, the at least
one functional group is selected from the group which consists of
acryl, methacryl, vinyl, allyl, ethinyl as well as further organic
groups with unsaturated functions.
[0116] Preferably, the organofunctional silane has at least one
acrylate and/or methacrylate group, because these can be reacted
with the acrylate or methacrylate compounds used to produce the
polyacrylate and/or polymethacrylate completely problem-free,
accompanied by the formation of a homogeneous plastic layer.
[0117] According to the invention, for example
(methacryloxymethyl)methyldimethoxysilane,
methacryloxymethyltrimethoxysilane,
(methacryloxymethyl)methyldiethoxysilane,
methacryloxymethyltriethoxysilane,
2-acryloxyethylmethyldimethoxysilane,
2-methacryloxyethyltrimethoxysilane,
3-acryloxypropylmethyldimethoxysilane,
2-acryloxyethyltrimethoxysilane,
2-methacryloxyethyltriethoxysilane,
3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltripropoxysilane,
3-methacryloxypropyltriethoxysilane,
3-methacryloxypropyltrimethoxysilane,
3-methacryloxypropyltriacetoxysilane,
3-methacryloxypropylmethyldimethoxysilane, vinyltrichlorosilane,
vinyl trimethoxysilane vinyldimethoxymethylsilane,
vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane,
vinyltriacetoxysilane or mixtures thereof can be used as
organofunctional silanes containing an acrylate and/or
methacrylate.
[0118] Such silanes can act as adhesion promoters between metal
oxide layer and plastic layer or between metal oxide layer,
preferably silicon oxide layer, and plastic layer. In other
embodiments, such silanes can also be at least partially
incorporated by polymerization into the plastic layer, as described
in WO 2008/095697 A1, which is included herewith by reference.
[0119] Within the framework of this invention, by a chemically
non-reactive plastic layer which "substantially consists of
polyacrylate and/or polymethacrylate" is meant that such a layer
can be modified by acrylate- and/or methacrylate-containing
silanes. The proportion of the quantities of the acrylate- and/or
methacrylate-containing silanes used corresponds at most to the
proportion of the quantities of the acrylate and/or methacrylate
monomers used. The molar ratio of acrylate- and/or
methacrylate-containing silanes to acrylate and/or methacrylate
monomers is preferably from 1:2 to 1:40, preferably from 1:3 to
1:30.
[0120] However, layers in which the acrylate- and/or
methacrylate-containing silanes are incorporated into the at least
one metal oxide layer, preferably silicon oxide layer, during a
sol-gel process are not a subject of this invention. Such layers
are described in EP 1812519 B1. It has been shown that, using the
technology described there, the layers cannot be produced in a
reliably reproducible manner, in order to give the
copper-containing platelet-shaped metal pigments the necessary
stabilities.
[0121] One or more further layers can also be arranged between the
copper-containing metal pigments and the at least one enveloping
metal oxide layer as well as the at least one chemically
non-reactive plastic layer. For example, a layer of copper oxide
can be arranged between the enveloping metal oxide layer and the
copper-containing metal pigments. This copper oxide layer can be
obtained for example by so-called fire-coloring in which
copper-containing pigments are heated in the presence of
atmospheric oxygen, accompanied by the formation of a colored
copper oxide layer. However, this oxidation must take place before
the application of the metal oxide layer, because the metal oxide
layer prevents the oxidation. Because of the intrinsic color and
because of interference effects, these copper oxide layers produce
widely different hues in the yellow-red color spectrum depending on
their layer thicknesses in the case of platelet-shaped metallic
effect pigments.
[0122] In the so-called fire treatment of copper-containing
metallic effect pigments, atmospheric oxygen acts on the
copper-containing metallic effect pigment over a defined period at
a defined temperature, whereby a thin copper oxide layer forms on
the copper-containing metal platelet. Interesting shades are
brought about by interference reflection. Fire-colored
copper-containing metallic effect pigments are traded commercially
inter alia in the hues English Green, Lemon, Deep Gold and in Fire
red colors. The fire-colored platelet-shaped, copper-containing
metal pigments, which are also called copper-containing metallic
effect pigments, are already protected against corrosion or
corrosive influences to a certain extent because of the copper
oxide layer produced by the heat treatment in the presence of
atmospheric oxygen.
[0123] The copper-containing metal pigment or the copper-containing
metal pigment provided with a copper oxide layer by fire-coloring
then has at least one enveloping metal oxide layer which is
different from copper oxide. The at least one enveloping metal
oxide layer which interacts synergistically with the chemically
non-reactive plastic layer therefore is not a copper oxide layer
within the meaning of the invention.
[0124] According to a preferred variant of the invention, the at
least one metal oxide layer which interacts synergistically with
the at least one chemically non-reactive plastic layer is not the
oxidation product of the uncoated copper-containing metal pigment.
The metal oxide layer which interacts synergistically with the at
least one chemically non-reactive plastic layer is preferably
applied in a separate step. The separate step can be for example a
wet-chemical coating or a gas-phase coating, for example by means
of PVD or CVD.
[0125] In particular very preferred embodiments of the invention,
the enveloping metal oxide layer(s) and the enveloping chemically
non-reactive plastic layer(s) follow one another directly. In
further particular, very preferred embodiments, it is furthermore
preferred that the enveloping metal oxide layer or the enveloping
chemically non-reactive plastic layer are applied directly to the
copper-containing metal pigment surface or directly to the copper
oxide layer.
[0126] In particular preferred embodiments, the copper-containing
metal pigments have, in addition to an optional copper oxide layer,
only one (1) enveloping metal oxide layer and only one (1)
enveloping chemically non-reactive plastic layer.
Determining Layer Thicknesses and Amount of Plastic Layer and Metal
Oxide Layer
[0127] The layer thicknesses of the metal oxide layers and of the
plastic layers on the copper-containing metal pigments are
determined for example by means of SEM pictures on suitable
cross-ground sections. Here, the pigments are applied in a varnish
and this is cured, Attention is to be paid here to as good as
possible an orientation of the platelets in the application medium.
For this, the metallic effect pigments can be pre-treated
beforehand by suitable additives. Then the cured varnish is sanded
and observed in SEM after usual sample preparation of the
cross-ground section. For the counting, only particles which have a
good orientation are selected. In this method, poorly-oriented
platelets yield a high error because of the unknown viewing angle.
The coatings have a very good contrast to the metal core. Should it
be impossible to distinguish well between the layer thicknesses of
the metal oxide layer and the plastic layer, locally resolved EDX
analyses can be used before the layer thicknesses are measured. The
term "average layer thickness" within the meaning of the invention
denotes the arithmetic average of the layer thicknesses of the
layers of at least 20 metal pigments. If the coating is irregular,
the arithmetic average of the thinnest and of the thickest points
of the coating of the respective particle is generated. Individual
serious deviations which affect for example the incorporation of
already coated finely dispersed pigments into the coating are not
taken into consideration in the calculation of the average layer
thickness.
[0128] The amount of metal oxide can take place via an elemental
analysis. Thus, for example in the case of an SiO.sub.2 layer, the
Si content can be determined in relation to the amount of the
copper-containing metal used as substrate and then projected onto
SiO.sub.2.
Producing Metallic Effect Pigments:
[0129] Preferably, the uncoated platelet-shaped copper-containing
metal pigments are obtained by grinding copper-containing grit, for
example copper or brass grit.
[0130] In the case of copper grit, highly pure, electrolytically
obtained copper is preferably used. Where necessary, the copper
grit is screened in order to obtain a desired size
distribution.
[0131] The copper-containing grit, for example brass grit, can have
a size distribution with a D.sub.grit,50 of from 1 to 220 .mu.m and
a D.sub.grit,90 of from 2 to 470 .mu.m. Such a grit is preferably
used in a dry grinding. The copper-containing grit, e.g. brass
grit, can also be converted to platelet-shaped copper-containing
pigments by wet grinding. After the grinding, a screening may be
necessary in order to obtain the desired uncoated platelet-shaped,
copper-containing metal pigment fraction.
[0132] The copper-containing metal grit can also contain zinc
and/or aluminum as well as further metals, in addition to copper.
For example, brass can contain 0.1 to 2 wt.-% aluminum, relative to
the weight of the uncoated copper-containing metal pigment.
[0133] In the case of brass grit, highly pure electrolytically
obtained copper and zinc are preferably used and preferably alloyed
by the addition of a little aluminum, as stated above, as reducing
agent. For this, copper and zinc are fused together and the
produced brass melt is atomized or nebulized into a brass grit. The
thus-obtained brass grit can then be screened, for example using a
cyclone, in order to obtain a starting brass grit with a desired
size distribution.
[0134] The brass grit preferably has a size distribution with a
D.sub.grit,50 in the range of from 1 to 220 .mu.m, preferably from
2 .mu.m to 190 .mu.m, more preferably from 4 to 150 .mu.m and still
more preferably from 6 .mu.m to 110 .mu.m, and a D.sub.grit,90 of
from 2 to 470 .mu.m, preferably from 3 .mu.m to 410 .mu.m, more
preferably from 6 to 360 .mu.m and still more preferably from 12 to
310 .mu.m.
[0135] The copper-containing metal grit with the desired size
distribution is subsequently ground to uncoated platelet-shaped
copper-containing metallic effect pigments.
[0136] The grinding of copper-containing metal grit, for example
copper or brass grit, takes place predominantly according to the
Hametag dry grinding process. Here, the copper-containing metal
grit, for example copper or brass grit, is ground in ball mills in
several grinding steps under different grinding conditions, such as
for example mill size, mill diameter, rotational speed of the mill,
ball size, grinding duration, with the addition of lubricant, such
as for example stearic or oleic acid, to prevent cold welding of
the copper-containing metal particles, for example copper or brass
particles, and with grinding bodies, such as e.g. steel balls. The
uncoated platelet-shaped copper-containing metallic effect pigments
are collected in different containers after the grinding and
optional screening and then homogenized or mixed.
[0137] In a wet grinding of copper-containing metal grit, for
example copper or brass grit, this is ground in the presence of
lubricant and solvent. A wet grinding is preferred, because this is
gentler than a dry grinding.
[0138] In particular preferred embodiments, the uncoated
platelet-shaped copper-containing metal pigments have, according to
a thickness computation using scanning electron microscopy (SEM),
an h.sub.50 value in a range of from 10 to 50 nm, preferably from
15 to 45 nm, particularly preferably from 15 to 40 nm and quite
particularly preferably from 20 to 35 nm.
[0139] Furthermore, in particular embodiments, the uncoated
platelet-shaped copper-containing metallic effect pigments have a
thickness distribution determined via thickness computation using
scanning electron microscopy (SEM) with an h.sub.90 value of from
20 to 70 nm, preferably from 20 to 60 nm, further preferably from
21 to 50 nm and particularly preferably from 22 to 40 nm.
[0140] In a furthermore preferred embodiment of the invention, the
uncoated platelet-shaped copper-containing metallic effect pigments
have an h.sub.10 value of the thickness distribution in the range
of from 8 to 25 nm and particularly preferably from 10 to 20
nm.
[0141] Furthermore, in particular preferred embodiments, the
uncoated platelet-shaped copper-containing metallic effect pigments
have a relative width of the thickness distribution .DELTA.h
determined via thickness computation using scanning electron
microscopy (SEM) which is calculated using the corresponding
cumulative breakthrough curve of the relative frequency according
to the formula
.DELTA.h=(h.sub.90-h.sub.10)/h.sub.50
of from 0.3 to 0.9, preferably from 0.35 to 0.85 and particularly
preferably from 0.4 to 0.8.
[0142] Furthermore, the uncoated platelet-shaped copper-containing
metallic effect pigments in particular preferred embodiments have
an aspect ratio of from 150 to 3,000. Preferably, the uncoated
platelet-shaped copper-containing pigments are characterized by an
aspect ratio of from 250 to 2,500, further preferably from 300 to
1,000 and particularly preferably from 325 to 600.
[0143] Further information on a grinding process that can be used
here is found in WO 2009/152941 A2, reference to the complete
disclosure content of which is made herewith.
[0144] In a further preferred embodiment, the copper-containing
grit particles, for example copper or brass particles, are ground
in two stages. The copper-containing grit particles, for example
copper or brass particles, are pre-deformed in the first stage and
ground in the second stage until the completely two-dimensionally
deformed uncoated platelet-shaped copper-containing metallic effect
pigments are obtained.
[0145] According to a further preferred variant of the invention,
uncoated copper effect pigments or uncoated brass effect pigments
obtained by physical vapor deposition, which are also called PVD
copper effect pigments or PVD brass effect pigments below, can also
be used. Such effect pigments are disclosed for example in EP 1 529
0784 B1 and EP 1 529 0785 B1.
[0146] PVD copper effect pigments or PVD brass effect pigments have
an absolutely flat surface. In this case, a coarse surface cannot
be produced by coating with metal oxide and a chemically
non-reactive plastic layer. These uncoated platelet-shaped
copper-containing metallic effect pigments according to the
invention produced using PVD copper effect pigments or PVD brass
effect pigments, after coating with the two-layered coating
according to the present invention, nevertheless have an excellent
resistance to corrosive influences from the surroundings and
prevent copper ions from being released into the surroundings.
[0147] Platelet-shaped copper-containing metal pigments according
to the invention prepared using PVD copper effect pigments or PVD
brass effect pigments are suitable with regard to the smooth
surface in particular for use in paints, printer inks, varnishes
and cosmetics. A use of the PVD copper effect pigments or PVD brass
effect pigments coated according to the invention in powder
coatings is less preferred.
Uses
Cosmetics
[0148] In cosmetic formulations, the platelet-shaped
copper-containing metal pigments according to the invention can be
combined with raw materials, auxiliary materials and active
ingredients suitable for the respective use. The concentration of
the platelet-shaped copper-containing metal pigments in the
formulation can lie between 0.001 wt.-% for rinse-off products and
40.0 wt.-% for leave-on products.
[0149] The platelet-shaped copper-containing metal pigments
according to the invention are suitable in particular for use in
cosmetics, such as e.g. body powder, face powder, pressed and loose
powder, face makeup, powder cream, cream makeup, emulsion makeup,
wax makeup, foundation, mousse makeup, blusher, eye makeup such as
eyeshadow, mascara, eyeliner, liquid eyeliner, eyebrow pencil, lip
balm, lipstick, lip gloss, lip liner, hair styling compositions
such as hair spray, hair mousse, hair gel, hair wax, hair mascara,
permanent or semi-permanent hair dyes, temporary hair dyes, skin
care compositions such as lotions, gels, emulsions as well as nail
polish compositions.
[0150] To achieve specific color effects, further coloring agents
and/or conventional effect pigments or mixtures thereof in variable
quantity ratios can be used in the cosmetic applications in
addition to the platelet-shaped copper-containing metal pigments
according to the invention. For example, pearlescent pigments
customary in the trade based on natural mica coated with highly
refractive metal oxides (such as e.g. the Prestige product group
from Eckart), BiOCl platelets, TiO.sub.2 platelets, pearlescent
pigments based on synthetic mica coated with highly refractive
metal oxides or based on glass platelets coated with highly
refractive metal oxides (such as e.g. the MIRAGE product group from
Eckart), Al.sub.2O.sub.3, SiO.sub.2 or TiO.sub.2 platelets can be
used as conventional effect pigments. In addition, metallic effect
pigments, such as e.g. the Visionaire product group from Eckart,
can also be added. The coloring agents can be selected from
inorganic or organic pigments.
Coating Agent
[0151] The object on which the invention is based is furthermore
achieved by providing a coating agent which contains
platelet-shaped copper-containing metal pigments according to the
invention.
[0152] According to a preferred variant of the present invention,
the coating agent is a varnish, such as e.g. a coil-coating
varnish, a varnish concentrate, a printer ink, a printer ink
concentrate, a paint, a paint concentrate, a powder coating or a
powder coating concentrate.
[0153] In the above-named coating agents, it is very advantageous
that the platelet-shaped copper-containing metal pigments according
to the invention release no noticeable quantities of copper ions,
preferably no copper ions, to the coating agent.
[0154] As stated at the outset, if copper ions are released to a
coating agent, there is the problem on the one hand that reduction
reactions result when copper(I) changes into the oxidation state
copper(II). On the other hand there is the problem that copper(II)
ions form colored complexes, for example strongly blue-colored
complexes with amines.
[0155] Naturally, such a discoloration of coating agents is
undesired.
[0156] The object on which the invention is based is furthermore
achieved by providing a coated object, wherein the coated object
contains or has platelet-shaped copper-containing pigments
according to the invention or a coating agent according to the
invention.
[0157] The coated objects can be car bodyworks, facade elements,
printed matter, such as for example printed films, paper, cardboard
boxes, plastic shaped parts, etc.
[0158] The object on which the invention is based is furthermore
achieved by the use of the platelet-shaped copper-containing metal
pigments according to the invention in a coating agent.
[0159] The copper-containing metal pigments according to the
invention have proved to be very advantageous for example in paints
and varnishes based on organic solvents or water. As a result of
their outstanding stability, they have proved to be particularly
suitable for applications in which for example a color stability
lasting years or decades under burdensome conditions is necessary.
For example, the pigments according to the invention are
well-suited to applications in which there is skin contact, and
external applications. Thus, for example, facade elements or mobile
phone shells can be colored with them.
[0160] In organic-based paints and varnishes, the pigments
according to the invention have proved to be very advantageous,
because for example an excellent long-term stability could be
achieved with them. This appears to be attributable to the reliable
inclusion of the copper ions, whereby undesired reactions of the
varnish constituents are avoided. However, use in water-based
paints and varnishes has also proved to be very advantageous, in
which a reliable coloring with long-term stability was achieved. It
is assumed that the particularly good water stability of the
copper-containing metal pigments according to the invention
prevents a reaction of the copper with the water, and thus a color
change, in the long term. The copper-containing metal pigments
according to the invention are therefore particularly well-suited
for example to use in aqueous dispersion paints such as wall
paints. In particular, forms of use such as application as a wall
paint also profit from the long-term stability in their applied
form. Thus, for example, no greenish or bluish discoloration as a
result of copper ions being discharged is observed even in the case
of moist walls.
[0161] Preferred coating agents containing the platelet-shaped
copper-containing metal pigments according to the invention are
water varnishes, powder coatings, nail polishes, polymers and
coil-coating formulations. In particular preferred embodiments, the
coating agent is a powder coating, a nail polish composition or a
varnish for use in the coil-coating process.
Powder Coating
[0162] Powder coatings are used for example in industrial series
production for coating electrically conductive and
temperature-resistant materials. The powder coating to be applied
is present here as a solid and solvent-free powder. Furthermore,
the powder coatings used as base coat or one-coat paint are almost
completely recyclable. The environmentally friendly and versatile
powder coatings contain binding agents, pigments, fillers and
cross-linkers as well as optionally additives. By a binding agent
is meant according to the invention the definition given in DIN 55
945. In other words, the binding agent comprises both the film
former and non-volatile excipients such as plasticizers and driers.
As a rule, the pulverulent powder coatings are deposited
electrostatically before they are hardened by baking or by
radiation energy.
[0163] Metallic effect pigments, inter alia, can be used to pigment
the powder coatings. In powder coatings produced by means of mixing
processes, however, it can prove to be problematic that damage to
or destruction of the pigment platelets can occur due to the
shearing forces acting on the pigment platelets during the
extrusion and grinding process. In particular, the luster and thus
also the visual effect of such pigmented applications can be
negatively affected by this.
[0164] For this reason, for example in the dry-blend process the
metallic effect pigments are admixed with the base powder coating
only after the grinding. However, this has the disadvantage that a
possible separation of pigment and powder coating occurs during the
varnish application due to the different loading behavior of the
individual varnish constituents. An irregular optical effect
results from this in the form of the depletion or accumulation of
pigment during the powder coating application. Furthermore, the
separation of pigment and binding agent leads to a modified
composition of the "overspray". Alternatively, the so-called
bonding method is used in which the pigment is fixed to the
particles of the base varnish under heating. However, the
production of such bonding powder coatings is relatively expensive.
The production of the currently most cost-favorable powder coatings
takes place using mixing methods. Here the pigments are mixed
together with all the other raw materials, extruded and ground.
[0165] Because substrates coated with powder coating are exposed to
temperatures of 200.degree. C. in a furnace after the powder
coating application, this results in copper-containing metal
pigments being oxidized, which manifests itself in an undesired
color change. It has been shown that even a very thick plastic
layer is unable to prevent the oxidation. However, such a plastic
layer brings about a good chemicals stability. Furthermore, it has
been shown that a metal oxide layer effectively prevents the
oxidation. However, the chemicals stability of such a layer is not
sufficient. The application of both layers in usual quantity
ratios, however, leads to a serious deterioration of the optical
properties. However, it has surprisingly been shown that the
desired stabilities are achieved by the coating to be applied
according to the invention, while the optical properties of the
pigment are almost or completely retained.
Coil-Coating
[0166] Coil-coating is also known as a very environmentally
friendly coating method. Here, coating and drying take place
continuously in a closed system, wherein the rinsing of chemical
residues can also be dispensed with in the no-rinse method.
Furthermore, an application efficiency of almost 100% can be
achieved by an optimized process control, while in other respects
in most varnishing methods there are for example greater losses due
to overspraying. However, because the varnish is baked at
temperatures of from 240 to 280.degree. C. in coil-coating, here
too oxidation phenomena are observed in conventional
copper-containing metal pigments analogously to powder coating. The
above-discussed problems and observations in relation to the powder
coating therefore also apply to coil-coating.
Nail Polish
[0167] Uncoated copper-containing pigments very readily release
copper ions which lead to a green discoloration e.g. in
nitrocellulose varnishes. In addition, the pigments settle at the
bottom over time and can no longer be shaken up or redispersed
after even a few days. Thus, the nail polish can no longer be used
after a few days. A metal oxide layer can curtail the release of
copper ions a little, but no satisfactory storage stabilities can
be achieved. However, it was surprisingly observed that
platelet-shaped copper-containing metal pigments which are coated
according to the invention with at least one plastic layer and at
least one metal oxide layer have storage stabilities over 6 months,
without a noticeable deterioration of the optical qualities,
compared with the uncoated pigment, occurring. Within the storage
time, the platelet-shaped copper-containing pigments according to
the invention which have settled at the bottom could always be
shaken up or easily redispersed again. Moreover, no green
discoloration appeared during the storage time.
Polymers
[0168] Copper-containing metal pigments incorporated into polymers,
in particular platelet-shaped copper-containing metal pigments, are
often oxidized during processing, whereby for example the color
changes. This can also be prevented only conditionally by changes
in the process conditions, whereby for example the reproduction of
a desired hue becomes almost impossible. It was surprisingly found
that the platelet-shaped copper-containing metal pigments according
to the invention have a sufficient stability in order to make
possible a processing under standard conditions, with the result
that no noticeable or no change whatever in the hue of the
platelet-shaped copper-containing metal pigments according to the
invention is observed.
[0169] The polymers used preferably comprise here thermoplastic,
thermosetting or elastomeric polymers. Thermoplastic polymers are
particularly preferred here.
[0170] All thermoplastics known to a person skilled in the art come
into consideration as thermoplastic polymers. Suitable
thermoplastic polymers are described for example in the
Kunststoff-Taschenbuch, ed. Saechtling, 25.sup.th edition,
Hanser-Verlag, Munich, 1992, in particular chapter 4 as well as
references cited therein, and in the Kunststoff-Handbuch, ed. G.
Becker and D. Braun, Volumes 1 to 11, Hanser-Verlag, Munich, 1966
to 1996.
[0171] By way of example, the following may be named as suitable
thermoplastics: polyoxyalkylenes, polycarbonates (PC), polyesters
such as polybutylene terephthalate (PBT) or polyethylene
terephthalate (PET), polyolefins such as polyethylene or
polypropylene (PP), poly(meth)acrylates, polyamides, vinylaromatic
(co)polymers such as polystyrene, impact-modified polystyrene such
as HIPS, or ASA, ABS or AES polymers, polyarylene ethers such as
polyphenylene ether (PPE), polysulfones, polyurethanes,
polylactides, halogen-containing polymers, polymers containing
imide groups, cellulose esters, silicone polymers or thermoplastic
elastomers. Mixtures of different thermoplastics can also be used
as materials for the polymer shaped parts. These mixtures can be
single- or multi-phase polymer blends.
[0172] The polymers can consist of identical or different
thermoplastics or thermoplastic blends.
[0173] Polyoxyalkylene homo- or copolymers, in particular
(co)polyoxymethylenes (POM), and methods for the production thereof
are known per se to a person skilled in the art and described in
the literature. Suitable materials are commercially available under
the brand name Ultraform.RTM. (BASF AG, Germany). Quite generally,
these polymers have at least 50 mol.-% recurring units of
--CH.sub.2O-- in the polymer main chain, The homopolymers are
generally produced by polymerization of formaldehyde or trioxane,
preferably in the presence of suitable catalysts. Polyoxymethylene
copolymers and polyoxymethylene terpolymers are preferred. The
preferred polyoxymethylene (co)polymers have melting points of at
least 150.degree. C. and molecular weights (weight-average value) M
in the range of from 5,000 to 200,000, preferably from 7,000 to
150,000 g.mu.mol. End-group-stabilized polyoxymethylene polymers
which have C--C bonds at the chain ends are particularly
preferred.
[0174] Suitable polycarbonates are known per se and can be obtained
e.g. according to DE-B-1 300 266 by interfacial polycondensation or
according to DE-A-14 95 730 by reacting biphenyl carbonate with
bisphenols. Preferred bisphenol is 2,2-di(4-hydroxyphenyl)propane,
generally called bisphenol A. The relative viscosity of these
polycarbonates generally lies in the range of from 1.1 to 1.5, in
particular 1.28 to 1.4 (measured at 25.degree. C. in a 0.5 wt.-%
solution in dichloromethane). Suitable polycarbonates are
commercially available under the brand name Lexan.RTM. (GE Plastics
B. V., Holland).
[0175] Suitable polyesters are also known per se and described in
the literature. They contain an aromatic ring in the main chain
which originates from an aromatic dicarboxylic acid. The aromatic
ring can also be substituted, e.g. by halogen such as chlorine and
bromine or by C.sub.1-C.sub.4 alkyl groups such as methyl, ethyl,
i- or n-propyl and n-, i- or tert-butyl groups. The polyesters can
be produced by reacting aromatic dicarboxylic acids, esters thereof
or other ester-forming derivatives of same with aliphatic dihydroxy
compounds in a manner known per se. Naphthaline dicarboxylic acid,
terephthalic acid and isophthalic acid or mixtures thereof are to
be named as preferred dicarboxylic acids. Up to 10 mol.-% of the
aromatic dicarboxylic acids can be replaced by aliphatic or
cycloaliphatic dicarboxylic acids such as adipic acid, azelaic
acid, sebacic acid, dodecane diacids and cyclohexane dicarboxylic
acids. Of the aliphatic dihydroxy compounds, dials with 2 to 6
carbon atoms, in particular 1,2-ethanediol, 1,4-butanediol,
1,6-hexanediol, 1,4-hexanedial, 1,4-cyclohexanediol and neopentyl
glycol or mixtures thereof are preferred. Polyalkylene
terephthalates which derive from alkanediols with 2 to 6 C atoms
are to be named as particularly preferred polyesters. Of these,
polyethylene terephthalate (PET), polyethylene naphthalate and
polybutylene terephthalate (PBT) are preferred in particular. These
products are commercially available e.g. under the trade names
Rynite.RTM. (PET; from DuPont, USA) or Ultradur.RTM. (PBT; BASF
AG). The viscosity number of the polyesters generally lies in the
range of from 60 to 200 ml/g (measured in a 0.5 wt.-% solution in a
phenolfo-dichlorobenzene mixture (wt. ratio 1:1 at 25.degree.
C.)).
[0176] Suitable polyolefins are quite generally represented by
polyethylene and polypropylene as well as copolymers based on
ethylene or propylene, optionally also with higher .alpha.-olefins.
Corresponding products can be obtained e.g. under the trade names
Lupolen.RTM. or Novolen.RTM.. By polyolefins are also meant
ethylene-propylene elastomers and ethylene-propylene
terpolymers.
[0177] Among the poly(meth)acrylates, in particular polymethyl
methacrylate (PMMA) as well as copolymers based on methyl
methacrylate with up to 40 wt.-% further copolymerizable monomers,
such as n-butyl acrylate, t-butyl acrylate or 2-ethylhexyl acrylate
are to be named, such as can be obtained for example under the
names Lucryl.RTM. (BASF AG) or Plexiglas.RTM. (Rohm GmbH, Germany).
Within the meaning of the invention, these also include
impact-modified poly(meth)acrylates as well as mixtures of
poly(meth)acrylates and SAN polymers which are impact-modified with
polyacrylate rubbers (e.g. the commercial product Terlux.RTM. from
BASF AG).
[0178] Suitable polyamides are those with aliphatic partially
crystalline or partially aromatic or amorphous structure of any
type and blends thereof, including polyetheramides such as
polyether block amides. By polyamides are meant all known
polyamides. Suitable polyamides generally have a viscosity number
of from 90 to 350, preferably 110 to 240 ml/g (determined in a 0.5
wt.-% solution in 96 wt.-% sulfuric acid at 25.degree. C. according
to ISO 307). Semi-crystalline or amorphous resins with a molecular
weight (weight-average value) of at least 5,000 g/mol, such as
described e.g. in U.S. Pat. Nos. 2,071,250, 2,071,251, 2,130,523,
2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210, are
preferred.
[0179] Examples of this are polyamides which derive from lactams
with 7 to 13 ring members, such as polycaprolactam,
polycapryllactam and polylauryllactam, as well as polyamides which
are obtained by reacting dicarboxylic acids with diamines.
[0180] Alkanedicarboxylic acids with 6 to 12, in particular 6 to 10
carbon atoms and aromatic dicarboxylic acids can be used as
dicarboxylic acids. Here, adipic acid, azelaic acid, sebacic acid,
dodecane diacid (=decanedicarboxylic acid) and/or isophthalic acid
may be named as acids.
[0181] Alkanediamines with 6 to 12, in particular 6 to 8 carbon
atoms, as well as m-xylylenediamine, di-(4-aminophenyl)methane,
di-(4-aminocyclohexyl)methane, 2,2-di-(4-aminophenyl)propane or
2,2-di-(4-aminocyclohexyl)propane are particularly suitable as
diamines.
[0182] Preferred polyamides are polyhexamethylene adipic acid amide
(PA 66), e.g. the commercial product Ultramid.RTM. A (BASF AG), and
polyhexamethylene sebacic acid amide (PA 610), e.g. the commercial
product Nylon.RTM. 610 (from DuPont), polycaprolactam (PA 6), e.g.
the commercial product Ultramid.RTM. B (BASF AG) as well as
copolyamide 6/66, in particular with a proportion of from 5 to 95
wt.-% caprolactam units, e.g. the commercial product Ultramid.RTM.
C (BASF AG). PA 6, PA 66 and copolyamide 6/66 are particularly
preferred.
[0183] Moreover, polyamides can also be used which can be obtained
e.g. by condensation of 1,4-diaminobutane with adipic acid at
increased temperature (polyamide-4,6). Production methods for
polyamides of this structure are described e.g. in EP-A 38 094, EPA
38 582 and EP-A 39 524.
[0184] Further examples are polyamides which can be obtained by
copolymerization of two or more of the above-named monomers, or
mixtures of several polyamides, wherein the mixing ratio is as
desired.
[0185] Furthermore, such partially aromatic copolyamides such as PA
6/6T and PA 66/6T the triamine content of which is less than 0.5,
preferably less than 0.3 wt.-% (see EP-A 299 444), have proved to
be particularly advantageous. The production of the partially
aromatic copolyamides with low triamine content can take place
according to the methods described in EP-A 129 195 and 129 196.
[0186] Further suitable thermoplastic materials are represented by
vinylaromatic (co)polymers. The molecular weight of these
commercially available polymers known per se generally lies in the
range of from 1,500 to 2,000,000, preferably in the range of from
70,000 to 1,000,000 g/mol.
[0187] By way of example, vinylaromatic (co)polymers of styrene,
chlorostyrene, .alpha.-methylstyrene and p-methylstyrene are named;
comonomers such as (meth)acrylonitrile or (meth)acrylic acid ester
can also be part of the structure in inferior proportions,
preferably not more than 20 wt.-%, in particular not more than 8
wt.-%. Particularly preferred vinylaromatic (co)polymers are
polystyrene, styrene-acrylonitrile copolymers (SAN) and
impact-modified polystyrene (HIPS=High Impact Polystyrene). It is
understood that mixtures of these polymers can also be used. The
production preferably takes place according to the method described
in EP-A-302 485.
[0188] Furthermore, ASA, ABS and AES polymers
(ASA=acrylonitrile-styrene-acrylester,
ABS=acrylonitrile-butadiene-styrene, AES=acrylonitrile-EPDM
rubber-styrene) are particularly preferred. These impact-resistant
vinylaromatic polymers contain at least one rubber elastic graft
polymer and a thermoplastic polymer (matrix polymer). Generally, a
styrene/acrylonitrile polymer (SAN) is used as matrix material.
Graft polymers are preferably used which contain, as rubber, [0189]
a diene rubber based on dienes, such as e.g. butadiene or isoprene,
(ABS); [0190] an alkyl acrylate rubber based on alkyl esters of
acrylic acid, such as n-butyl acrylate and 2-ethylhexyl acrylate,
(ASA); [0191] an EPDM rubber based on ethylene, propylene and a
diene, (AES); or mixtures of these rubbers or rubber monomers.
[0192] The production of suitable ABS polymers is found e.g.
described in detail in the German patent application DE-A 19728629.
For the production of ASA polymers, EP-A 99 532 can e.g. be
consulted. Details on the production of AES polymers are disclosed
for example in U.S. Pat. No. 3,055,859 or in U.S. Pat. No.
4,224,419. Reference is hereby made expressly to the patent
specifications named in this paragraph.
[0193] By polyarylene ethers are preferably meant both polyarylene
ethers per se and polyarylene ether sulfides, polyarylene ether
sulfones or polyarylene ether ketones. The arylene groups thereof
can be the same or different and independently of each other mean
an aromatic radical with 6 to 18 C atoms. Examples of suitable
arylene radicals are phenylene, bisphenylene, terphenylene,
1,5-naphthylene, 1,6-naphthylene, 1,5-anthrylene, 9,10-anthrylene
or 2,6-anthrylene. Of these, 1,4-phenylene and 4,4'-biphenylene are
preferred. These aromatic radicals are preferably not substituted.
However, they can carry one or more substituents. Suitable
polyphenylene ethers are commercially available under the name
Noryl.RTM. (GE Plastics B. V., Holland).
[0194] In general, the polyarylene ethers have average molecular
weights M (numerical average) in the range of from 10,000 to 60,000
g/mol and viscosity numbers of from 30 to 150 ml/g. The viscosity
numbers are measured depending on the solubility of the polyarylene
ethers either in 1 wt.-% N-methylpyrrolidone solution, in mixtures
of phenol and o-dichlorobenzene or in 96% sulfuric acid at in each
case 20.degree. C. and 25.degree. C.
[0195] The polyarylene ethers are known per se or can be produced
according to methods known per se.
[0196] Preferred process conditions for the synthesis of
polyarylene ether sulfones or ketones are described for example in
EP-A 113 112 and EP-A 135 130. As a rule, polyarylene ether
sulfones have a melting point of at least 320.degree. C.,
polyarylene ether ketones have a melting point of at least
370.degree. C. Suitable polyphenylene ether sulfones are
commercially available e.g. under the name Ultrason.RTM. E (BASF
AG), suitable polyphenylene ether ketones under the name
Victrex.RTM..
[0197] In addition, polyurethanes, polyisocyanurates and polyureas
are suitable for coloring with platelet-shaped copper-containing
metal pigments according to the invention. Soft, semi-hard or hard
thermoplastic or cross-linked polyisocyanate polyaddition products,
for example polyurethanes, polyisocyanurates and/or polyureas, in
particular polyurethanes, are generally known and commercially
available i.a. under the name Elastolan.RTM. (Elastogran GmbH,
Germany). Their production is widely described and usually takes
place by reacting isocyanates with compounds reactive vis-a-vis
isocyanates under generally known conditions. The reaction is
preferably carried out in the presence of catalysts and/or
excipients. If foamed polyisocyanate polyaddition products are
involved, these are produced in the presence of usual foaming
agents.
[0198] The aromatic, arylaliphatic, aliphatic and/or cycloaliphatic
organic isocyanates known per se, preferably diisocyanates, come
into consideration as isocyanates.
[0199] For example, generally known compounds with a molecular
weight of from 60 to 10,000 g/mol and a functionality vis-a-vis
isocyanates of from 1 to 8, preferably 2 to 6, can be used as
compounds reactive vis-a-vis isocyanates (in the case of
thermoplastic polyurethanes TPU functionality approx. 2), for
example polyols with a molecular weight of from 500 to 10,000
glmol, e.g. polyether polyols, polyester polyols,
polyetherpolyester polyols, and/or diols, triols and/or polyols
with molecular weights smaller than 500 g/mol.
[0200] Polylactides, thus polymers of lactic acid, are known per se
or can be produced according to methods known per se and can also
be used in conjunction with the platelet-shaped copper-containing
metal pigments according to the invention. In addition to
polylactide, co- or block copolymers based on lactic acid and
further monomers can also be used. Linear polylactides are usually
used. However, branched lactic acid polymers can also be used. For
example, multifunctional acids or alcohols can serve as branching
agents.
[0201] In particular, polymers of vinyl chloride are to be named as
suitable halogen-containing polymers, in particular polyvinyl
chloride (PVC) such as hard PVC and soft PVC, and copolymers of
vinyl chloride such as PVC-U molding compounds.
[0202] Furthermore, fluorine-containing polymers come into
consideration, in particular polytetrafluoroethylene (PTFE),
tetrafluoroethylene-perfluoropropylene copolymers (FEP), copolymers
of tetrafluoroethylene with perfluoroalkylvinylether,
ethylene-tetrafluoroethylene copolymers (ETFE); polyvinylidene
fluoride (PVDF), polyvinyl fluoride (PVF),
polychlorotrifluoroethylene (PCTFE), and
ethylene-chlorotrifluoroethylene copolymers (ECTFE).
[0203] Polymers containing imide groups are in particular
polyimides, polyetherimides, and polyamide-imides.
[0204] Suitable cellulose esters are for instance cellulose
acetate, cellulose acetobutyrate, and cellulose propionate.
[0205] In addition, silicone polymers also come into consideration
as thermoplastics. Silicone rubbers are suitable in particular.
These are usually polyorganosiloxanes which have groups capable of
cross-linking reactions.
[0206] Such polymers are described for example in Rompp Chemie
Lexikon, CD-ROM version 1.0, Thieme Verlag Stuttgart 1995.
[0207] The platelet-shaped copper-containing metal pigments
according to the invention can also be introduced into
thermoplastic elastomers (TPE). TPEs can be processed like
thermoplastics, but have rubber-elastic properties. TPE block
polymers, TPE graft polymers and segmented TPE copolymers of two or
more monomer building blocks are suitable. Particularly suitable
TPEs are thermoplastic polyurethane elastomers (TPE-U or TPU),
styrene oligoblock copolymers (TPE-S) such as SBS
(styrene-butadiene-styrene-oxy block copolymer) and SEES
(styrene-ethylene-butylene-styrene block copolymers, available by
hydrogenation of SBS), thermoplastic polyolefin elastomers (TPE-O),
thermoplastic polyester elastomers (TPE-E), thermoplastic polyamide
elastomers (TPE-A) and in particular thermoplastic vulcanisates
(TPE-V). A person skilled in the art will find details on TPEs in
G. Holden et al., Thermoplastic Elastomers, 2.sup.nd edition,
Hanser Verlag, Munich 1996.
[0208] In addition to the platelet-shaped copper-containing
metallic effect pigments according to the invention, usual
additives can furthermore be contained in the polymers. These
additives can be selected for example from the group which consists
of fillers, additives, plasticizers, lubricants or mold release
agents, impact modifiers, pigments, dyes, flame retardants, static
inhibitors, optical brighteners, antioxidants, antimicrobial
biostabilizers, chemical foaming agents or organic cross-linking
agents as well as other additives and mixtures thereof.
[0209] It was found that, below 0.1 wt.-% of the platelet-shaped
copper-containing metal pigments according to the invention,
relative to the total weight of the polymer containing metal
pigment, the coloring effect is much less pronounced. Furthermore,
it was found that, above 10 wt.-%, relative to the total weight of
the polymer containing metal pigment, the mechanical strength
decreases. According to particular preferred embodiments, the
proportion of the platelet-shaped copper-containing metal pigments
according to the invention in the polymer is 0.01 to 10 wt.-%,
preferably 0.1 to 8 wt.-%, in each case relative to the total
weight of the polymer containing metal pigment. In addition, it is
preferred that the proportion of the platelet-shaped
copper-containing metal pigments according to the invention in the
polymer is 0.25 to 5 wt.-%, still further preferably 0.5 to 2.5
wt.-%, in each case relative to the total weight of the polymer
containing metal pigment.
[0210] The plastics containing the platelet-shaped
copper-containing metal pigment according to the invention can also
be used in laser marking. During irradiation, the laser beam heats
the platelet-shaped copper-containing metal pigments according to
the invention struck by it, which then lead to a visible change in
the plastic surrounding the metal pigments.
[0211] It has been established that the possibility of laser
marking greatly diminishes below 0.0005 wt.-%, relative to the
total weight of the polymer containing the platelet-shaped
copper-containing metal pigment according to the invention. On the
other hand, the optical properties of the polymer are already
greatly influenced at a concentration of more than 0.7 wt.-%,
relative to the total weight of the polymer containing the
platelet-shaped copper-containing metal pigment according to the
invention. According to particular preferred embodiments, the
proportion of the platelet-shaped copper-containing metal pigments
in the polymer is therefore 0.0005 to 0.7 wt.-%, preferably 0.001
to 0.5 wt.-%, in each case relative to the total weight of the
polymer containing metal pigment. In addition, it is preferred in
particular embodiments that the proportion of the platelet-shaped
copper-containing metal pigments according to the invention is
0.005 to 0.5 wt.-%, still further preferably 0.01 to 0.1 wt.-%, in
each case relative to the total weight of the polymer containing
metal pigment.
Methods:
[0212] The object of the invention is furthermore achieved by
providing a method for producing a copper-containing pigment
according to the invention, wherein the method comprises the
following steps:
[0213] (1a) coating platelet-shaped copper-containing metal
pigments with metal oxide,
[0214] (1b) coating the platelet-shaped copper-containing metal
pigments coated with metal oxide obtained in step (1a) with the
educt(s) of the chemically non-reactive plastic layer,
[0215] (1c) curing or polymerizing the copper-containing metal
pigments coated with the educt(s) of the chemically non-reactive
plastic layer in step (1b) or
[0216] (2a) coating platelet-shaped copper-containing metal
pigments with the educt(s) of the chemically non-reactive plastic
layer,
[0217] (2b) curing or polymerizing the platelet-shaped
copper-containing metal pigments coated with the educt(s) of the
chemically non-reactive plastic layer in step (2a),
[0218] (2c) coating the platelet-shaped copper-containing metal
pigments coated with chemically non-reactive plastic layer obtained
in step (2b) with metal oxide.
[0219] The platelet-shaped copper-containing metal pigments
obtained in step (1c) or step (2b) then have a chemically
non-reactive plastic layer.
[0220] In particular preferred embodiments, the above-named
coatings with metal oxide and/or the chemically non-reactive
plastic layer are carried out repeatedly or with other metal oxides
or educts of a chemically non-reactive plastic layer, in order to
provide a coating with several metal oxide layers and/or chemically
non-reactive plastic layers.
[0221] The coating of the platelet-shaped copper-containing metal
pigments with metal oxide can be carried out in a conventional
manner. For example, the metal oxides can be applied accompanied by
hydrolysis of corresponding metal salts, such as for example metal
halides, in particular metal chlorides.
[0222] The metal oxide layers are preferably applied by means of
sol-gel methods. Here, the corresponding metal alkoxides are
hydrolyzed accompanied by the addition of water, as well as
preferably acids or bases as catalysts, wherein the corresponding
metal oxides and/or metal oxide hydrates are deposited on the
copper-containing metal pigments and cover them.
[0223] The alkoxy groups are preferably methoxy, ethoxy, propoxy,
butoxy and/or pentoxy groups. The alkoxy groups are extremely
preferably methoxy and/or ethoxy groups.
[0224] The coating with metal oxide by means of sol-gel methods
usually takes place in organic solvent in the presence of small
quantities of water, such as for example 1 to 10 vol.-%, preferably
2 to 5 vol.-%, water, relative to the total volume of the
water-containing organic solvent.
[0225] Alcohols, glycols, esters, ketones as well as mixtures of
these solvents are preferably used as organic solvents. The use of
alcohols, glycols or mixtures thereof is particularly suitable.
Alcohols are particularly preferably used.
[0226] The alcohol is preferably selected from the group which
consists of methanol, ethanol, isopropanol, n-propanol, t-butanol,
n-butanol, isobutyl alcohol, pentanol, hexanol and mixtures
thereof. Ethanol and/or isopropanol have proved to be very
suitable.
[0227] Butyl glycol, propyl glycol, ethylene glycol or mixtures
thereof are preferably used as glycol.
[0228] The platelet-shaped copper-containing metal pigments are
dispersed in the organic solvent accompanied by the optional
addition of water. Either acid or base is added, as catalyst, to
this suspension.
[0229] The dispersion is preferably heated. The water necessary for
hydrolysis can be already contained in the organic solvent or added
at a later point in time.
[0230] The acid can be organic and/or inorganic acid. The organic
acid is preferably selected from the group which consists of formic
acid, acetic acid, propanoic acid, oxalic acid, malonic acid,
maleic acid, succinic acid, anhydrides of the named acids and
mixtures thereof. Formic acid, acetic acid, oxalic acid or mixtures
thereof are preferably used.
[0231] The inorganic acid can be selected be selected from the
group which consists of nitric acid, sulfuric acid, phosphoric
acid, hydrochloric acid, boric acid, hydrofluoric acid and mixtures
thereof. Nitric acid and/or hydrofluoric acid are preferably
used.
[0232] According to a preferred variant, the basic catalyst is an
amine. This can be primary, secondary or tertiary amines.
[0233] According to a preferred embodiment, the amine is selected
from the group which consists of dimethylethanolamine (DMSA),
monoethanolamine (MEA), diethanolamine (DEA), triethanolamine
(TEA), ethylenediamine (EDA), t-butylamine, monomethylamine,
dimethylamine, trimethylamine, monoethylamine, diethylamine,
triethylamine, diisopropylethylamine, pyridine, pyridine
derivatives, aniline, aniline derivatives, choline, choline
derivatives, urea, urea derivative, hydrazine derivatives and
mixtures thereof.
[0234] Ethylenediamine, monoethylamine, diethylamine,
monomethylamine, dimethylamine, triethylamine or mixtures thereof
have proved to be very suitable as basic aminic catalyst.
[0235] Of course, inorganic bases, such as ammonia, hydrazine,
sodium hydroxide, potassium hydroxide, ammonium hydroxide, ammonium
carbonate, ammonium hydrogen carbonate, sodium carbonate, sodium
hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate
or mixtures thereof can also be used. Ammonia and/or hydrazine have
proved to be very suitable.
[0236] According to an extremely preferred embodiment,
tetraalkoxysilane is used as metal alkoxide. Tetramethoxysilane,
tetraethoxysilane, tetraisopropoxysilane or condensates thereof or
mixtures thereof are preferably used as tetraalkoxysilane.
Tetraethoxysilane and/or oligomers of tetraethoxysilane have proved
to be very suitable.
[0237] After application of the metal oxide layer, the
platelet-shaped copper-containing metal pigments coated with metal
oxide are preferably separated and the chemically non-reactive
plastic layer is applied. The chemically non-reactive plastic layer
can be constructed by polymerization of suitable monomers. The
monomers can have functionalities which are selected from the group
which consists of amino, hydroxy, thiol, epoxy, acrylate,
methacrylate, vinyl, allyl, alkenyl, alkynyl, carboxy, carboxyl
anhydride, isocyanate, cyanate, ureido, carbamate, ester groups and
mixtures thereof.
[0238] In particular cross-linking, i.e. multifunctional
(meth)acrylates, as monomers or reactive oligomers or polymers, are
suitable as educts of the plastic layer. Examples of such compounds
are:
[0239] allyl methacrylate, bisphenol A dimethacrylate,
1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate,
ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate,
1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate,
diurethane dimethacrylate, dipropylene glycol diacrylate,
1,12-dodecanediol dimethacrylate, ethylene glycol dimethacrylate,
methacrylic acid anhydride, N,N-methylene-bis-methacrylamide,
neopentyl glycol dimethacrylate, polyethylene glycol
dimethacrylate, polyethylene glycol 200 diacrylate, polyethylene
glycol 400 diacrylate, polyethylene glycol 400 dimethacrylate,
tetraethylene glycol diacrylate, tetraethylene glycol
dimethacrylate, tricyclodecane dimethanol diacrylate, tripropylene
glycol diacrylate, triethylene glycol dimethacrylate,
pentaerythritol triacrylate, trimethyloipropane triacrylate,
trimethylolpropane trimethacrylate,
tris-(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol
tetraacrylate, dipentaerythritol pentaacrylate or mixtures
thereof.
[0240] In particular embodiments, tri- and higher functional
(meth)acrylates, in particular trifunctional (meth)acrylates, are
preferred. The term "(meth)acrylate" within the meaning of the
present invention comprises methacrylates and acrylates.
[0241] The curing or polymerization of vinyl- and/or
(meth)acrylate-functional monomers during the production of the
chemically non-reactive plastic layer can take place thermally in
preferred embodiments.
[0242] In further preferred embodiments, the curing or
polymerization takes place by radical polymerization using
polymerization initiators, preferably radical initiators. These are
peroxides or diazonium compounds that are customary in the trade
and as a rule organic or inorganic. Examples of such compounds
are:
[0243] acetylcyclohexane sulfonyl peroxide,
bis(2,4-dichlorobenzoyl)peroxide, diisononanyl peroxide, dioctanoyl
peroxide, diacetyl and dibenzoyl peroxide; peroxydicarbonates (e.g.
diisopropyl peroxydicarbonate, di-n-butyl peroxydicarbonate,
di-2-ethylhexyl peroxydicarbonate, dicyclohexyl peroxydicarbonate),
alkyl perester (e.g. cumyl perneodecanoate, t-butyl
perneodecanoate, t-amyl perpivalate, t-butyl per-2-ethylhexanoate,
t-butyl perisobutyrate, t-butyl perbenzoate), dialkyl peroxides
(e.g. dicumyl peroxide, t-butylcumyl peroxide,
2,5-dimethylhexane-2,5-di-t-butyl peroxide, di(t-butylperoxy
isopropyl)benzene, di-t-butyl peroxide, or 2,5-dimethyl
hexine-3-2,5-di-t-butyl peroxide), perketals (e.g.
1,1-bis-(t-butylperoxy)-3,3,5-trimethylcyclohexanone peroxide,
methyl isobutyl ketone peroxide, methyl ethyl ketone peroxide,
acetyl acetone peroxide), alkyl hydroperoxides (e.g. pinane
hydroperoxide, cumolhydroperoxide,
2,5-dimethylhexane-2,5-dihydroperoxide or t-butyl hydroperoxide),
azo compounds (e.g. 4-4'-azobis(4-cyanovaleric acid),
1,1'-azobis(cyclohexanecarboxylic acid nitrile),
1,1'-azobis(isobutyro acid amidine)dihydrochloride,
2,2'-azobis(isobutyronitrile), dimethyl
2,2'-azobis(2-methylpropionate) or persulfates such as sodium
peroxodisulfate and potassium peroxodisulfate.
2,2'-azobis(isobutyronitrile) and dimethyl
2,2'-azobis(2-methylpropionate) are preferred. These compounds are
commercially available from Aldrich Chemie, D-89552, Steinheim or
Wako Chemicals GmbH, Fuggerstra.beta.e 12, 41468 Neuss.
[0244] The educts of the plastic layer, for example reactive
oligomers and/or polymers, can also reactive polymers which are
selected from the group which consists of polyacrylates,
poly(meth)acrylates, polyethers, polyesters, polyamines,
polyamides, polyols, polyurethanes, polyolefins and mixtures
thereof.
[0245] According to a variant of the invention, the platelet-shaped
copper-containing metal pigments coated with metal oxide are
dispersed in a, preferably organic, solvent and the suspension is
brought to reaction temperature. The educts of the plastic layer
are then added, for example in the form of organic monomers and/or
reactive oligomers/polymers, as well as optionally polymerization
initiators, for example by dropwise addition, whereby the
chemically non-reactive plastic layer (organic polymer layer) is
formed on the copper-containing pigments coated with metal oxide.
The dispersion is preferably stirred or moved during the
application of the plastic layer.
[0246] Of course, the chemically non-reactive plastic layer can
also be applied by spraying the educts of the plastic layer, for
example the organic monomers and/or reactive organic oligomers
and/or reactive organic polymers, as well as optionally
polymerization initiators, in a fluidized bed in which the
copper-containing metal pigments coated with metal oxide are
swirled.
[0247] According to a preferred variant of the invention, the
coating takes place in a liquid phase.
[0248] According to a further variant of the invention, the
application of the chemically non-reactive plastic layer takes
place in the same solvent in which the metal oxide layer was
applied. This method variant is a one-step method, unlike the
above-described two-step method variant.
[0249] After application of the chemically non-reactive plastic
layer, these are preferably filtered off from the suspension.
[0250] According to a further variant of the invention, the
application of the chemically non-reactive plastic layer to the
metal oxide layer takes place in the form of a thermal
polymerization. It has been observed that in the case of this
thermal polymerization, which is carried out without the addition
of an initiator, smooth surfaces result.
[0251] According to a further variant of the invention, the
application of the layers takes place in reverse order, i.e. the
chemically non-reactive plastic layer is applied first and then the
metal oxide layer.
[0252] The platelet-shaped copper-containing metal pigments
according to the invention are preferably pelletized, granulated,
extrusion-granulated, extruded, briquetted, tableted and are
therefore present in a substantially low-dust, preferably
dust-free, compacted form. The copper-containing metal pigments
according to the invention can be easily handled in these dosage
forms and are easily incorporated into coating agents, such as for
example varnishes, paints, printer inks, powder coatings, plastics,
cosmetics, etc.
[0253] According to a preferred variant, the platelet-shaped
copper-containing metal pigments according to the invention are
incorporated into powder coating.
[0254] According to a preferred variant of the invention, the
chemically non-reactive plastic layer of the platelet-shaped
copper-containing metal pigments is compatible with the binding
agent or binding agent system of the powder coating.
[0255] The invention is described in more detail below with
reference to examples, without being limited thereto.
EXAMPLES
Example 1
Example 1a
Metal Oxide Layer
[0256] 250 g rich pale gold G900 (Eckart GmbH, Hartenstein,
Germany) was dispersed in 500 g ethanol. After heating to
50.degree. C., 26 g tetraethoxysilane (TEOS) was added. 80 ml of a
3% ammonia solution was then added over 3 h. Stirring followed for
a further hour, the reaction mixture was filtered off and the
product obtained as a paste.
Example 1b
Plastic Layer (Initiator Variant)
[0257] 139 g of the paste obtained in Example 1a (rich pale gold G
900 encapsulated with metal oxide) (corresponds to 100 g metal
pigment) was dispersed in 486 g ethanol, with the result that a 16
M.-% dispersion formed. 1 g methacryloxypropyltrimethoxysilane
(MEMO) was then added and the mixture was stirred for 30 min at
25.degree. C. and for 1 h at 75.degree. C. 250 ml of a solution of
1.5 g dimethyl 2,2'-azobis(2-methylpropionate) (trade name V 601;
available from WAKO Chemicals GmbH, Fuggerstra.beta.e 12, 41468
Neuss), 4.75 g methacryloxypropyltrimethoxysilane (MEMO) and 17.5 g
trimethylolpropane trimethacrylate (TMPTMA) in white spirit was
then added to the reaction mixture over 1 h. Stirring followed for
a further 15 h at 75.degree. C., the reaction mixture was filtered
off and isolated as paste.
Example 1c
Plastic Layer (Thermal Variant)
[0258] 139 g of the paste obtained in Example 1a (rich pale gold
G900 encapsulated with metal oxide) (corresponds to 100 g metal
pigment) was dispersed in 486 g white spirit D100, with the result
that a 16 wt.-% dispersion formed. 1 g
methacryloxypropyltrimethoxysilane (MEMO) was then added and the
mixture was stirred for 15 min at 25.degree. C. and for 3 h at
50.degree. C. 240 ml of a solution of 5.8 g
methacryloxypropyltrimethoxysilane (MEMO) and 17.5 g
trimethylolpropane trimethacrylate (TMPTMA) in white spirit 0100
was then added at 130.degree. C. over 2 h. After 15 h of stirring
at 130.degree. C., the reaction mixture was filtered off, washed
with 800 ml white spirit D100 and isolated as paste.
Example 2
[0259] 100 g pale gold Dorolan L 900 (Eckart GmbH, Hartenstein,
Germany) was dispersed in 525 g white spirit D100, with the result
that a 16 wt.-% dispersion formed. 1 g
methacryloxypropyltrimethoxysilane (MEMO) was then added and the
mixture was stirred for 1 h at 25.degree. C. and for 3 h at
50.degree. C. 240 ml of a solution of 4.6 g
methacryloxypropyltrimethoxysilane (MEMO) and 13.75 g
trimethylolpropane trimethacrylate (TMPTMA) in white spirit D100
was then added over 2 h at 130.degree. C. Stirring followed for a
further 15 h at 130.degree. C., the reaction mixture was filtered
off and isolated as paste.
Example 3
[0260] 100 g fire red Dorolan L900 (Eckart GmbH, Hartenstein,
Germany) was dispersed in 525 g white spirit D100, with the result
that a 16 wt.-% dispersion formed. 1 g
methacryloxypropyltrimethoxysilane (MEMO) was then added and the
mixture was stirred for 1 h at 25.degree. C. and for 3 h at
50.degree. C. 240 ml of a solution of 19.35 g trimethylolpropane
trimethacrylate (TMPTMA) in white spirit D100 was then added over 2
h at 130.degree. C. Stirring followed for a further 15 h at
130.degree. C., the reaction mixture was filtered off and isolated
as paste.
Example 4
[0261] Analogously to Example 3, the same coating was carried out
with copper Dorolan L900.
Example 5
[0262] 100 g copper Dorolan L900 (Eckart GmbH, Hartenstein,
Germany) was dispersed in 525 g white spirit D100, with the result
that a 16 wt.-% dispersion formed. 1 g
methacryloxypropyltrimethoxysilane (MEMO) was then added and the
mixture was stirred for 1 h at 25.degree. C. and for 3 h at
50.degree. C. 240 ml of a solution of 18.35 g trimethylolpropane
trimethacrylate (TMPTMA) in white spirit D100 was then added over 3
h at 130.degree. C. The end of the addition was followed by
stirring for a further 15 h at 130.degree. C., the reaction mixture
was filtered off and isolated as paste.
Example 6
[0263] 100 g fire red Dorolan L 900 (Eckart GmbH, Hartenstein,
Germany) was dispersed in 525 g white spirit D100, with the result
that a 16 wt.-% dispersion formed. 1 g
methacryloxypropyltrimethoxysilane (MEMO) was then added and the
mixture was stirred for 1 h at 25.degree. C. and for 3 h at
50.degree. C. 240 ml of a solution of 18.35 g trimethylolpropane
trimethacrylate (TMPTMA) in white spirit D100 was then added over 3
h at 130.degree. C. The end of the addition was followed by
stirring for a further 15 h at 130.degree. C., the reaction mixture
was filtered off and isolated as paste.
Example 7
[0264] 100 g fire red Dorolan L 900 (Eckart GmbH, Hartenstein,
Germany) was dispersed in 525 g white spirit, with the result that
a 16 wt.-% dispersion formed. 1 g
methacryloxypropyltrimethoxysilane (MEMO) was then added and the
mixture was stirred for 1 h at 25.degree. C. and for 3 h at
50.degree. C. 240 ml of a solution of 12.85 g trimethylolpropane
trimethacrylate (TMPTMA) in white spirit D00 was then added over 3
h at 130.degree. C. The end of the addition was followed by
stirring for a further 15 h at 130.degree. C., the reaction mixture
was filtered off and isolated as paste.
Example 8
Example 8a
Plastic Layer
[0265] 200 g rich pale gold RBIG G900 (Eckart GmbH, Hartenstein,
Germany) was dispersed in 1050 g ethanol, with the result that a 16
wt.-% dispersion formed. 1.3 g methacryloxypropyltrimethoxysilane
(MEMO) and 4 g trimethylolpropane trimethacrylate (TMPTMA) were
then added and the mixture was stirred for 1 h at 25.degree. C. and
for 3 h at 50.degree. C. 100 ml of a solution of 42 g
trimethylolpropane trimethacrylate (TMPTMA) and 1 g dimethyl
2,2'-azobis(2-methylpropionate) (trade name V 601; available from
WAKO Chemicals GmbH, Fuggerstr.beta.e 12, 41468 Neuss) in ethanol
was then added over 3 h at 75.degree. C. Stirring followed for a
further 15 h at 75.degree. C., the reaction mixture was filtered
off and isolated as paste.
Example 8b
Metal Oxide Layer
[0266] 104 g of the paste obtained in Example 8 (corresponds to 70
g pigment) was dispersed in 316 g ethanol, with the result that a
solids content of 16.7 wt.-% results. 23.3 g tetraethoxysilane
(TEOS) was then added and the reaction mixture was heated to
75.degree. C. 100 ml of a solution of 2 g ethylenediamine (EDA) and
20 g water in ethanol was then added over 3 h at 75.degree. C.
Stirring followed for 15 h at 75.degree. C., the reaction mixture
was filtered off and the product obtained as a paste.
Example 9
Example 9a
Plastic Layer
[0267] 200 g rich pale gold G900 (Eckart GmbH, Hartenstein,
Germany) was dispersed in 1050 g ethanol, with the result that a 16
wt.-% dispersion formed. 1.3 g methacryloxypropyltrimethoxysilane
(MEMO) was then added and the mixture was stirred for 1 h at
25.degree. C. and for 3 h at 75.degree. C. 100 ml of a solution of
28 g trimethylolpropane trimethacrylate (TMPTMA) and 0.9 g dimethyl
2,2'-azobis(2-methylpropionate) (trade name V 601; available from
WAKO Chemicals GmbH, Fuggerstra.beta.e 12, 41468 Neuss) in ethanol
was then added over 3 h at 75.degree. C. Stirring followed for 15 h
at 75.degree. C., the reaction mixture was filtered off and
isolated as paste.
Example 9b
Metal Oxide Layer
[0268] 103 g of the paste obtained in Example 9a (corresponds to 70
g pigment) was dispersed in 333 g ethanol, with the result that a
solids content of 16 wt.-% resulted. 7.56 g tetraethoxysilane
(TEOS) was then added at 75.degree. C. 100 ml of a solution of 0.65
g ethylenediamine (FDA) and 21 g water in ethanol was then added at
75.degree. C. Stirring followed for 15 h at 75.degree. C., the
reaction mixture was filtered off and the product obtained as a
paste.
Example 10
[0269] Analogously to the conditions described under Example 8
and/or 9, different coated platelet-shaped copper-containing metal
pigments were produced.
TABLE-US-00001 TABLE 1 Educt quantities of Examples 10-1 to 10-11
TMPTMA TMPTMA Procedure 1st 2nd analogous to MEMO addition addition
TEOS CE 10-1 8a, 9b 1.3 g 4.0 g 8 g 8.1 g CE 10-2 8a, 9b 1.3 g 4.0
g 8 g 13.1 g CE 10-3 8a, 9b 1.3 g 4.0 g 8 g 18.8 g Example 10-4 8a,
9b 1.3 g 4.0 g 24 g 3.8 g Example 10-5 9a, 9b 1.3 g 4.0 g 24 g 8.0
g Example 10-6 8a, 9b 1.3 g 4.0 g 42 g 2.5 g Example 10-7 8a, 9b
1.3 g 4.0 g 42 g 7.5 g Example 10-8 8a, 9b 1.3 g 4.0 g 42 g 23.3 g
CE 10-9 8a 1.3 g 4.0 g 87 g -- CE 10-10 8a, 9b 1.3 g 4.0 g 60 g 2 g
CE 10-11 8a, 9b 1.3 g 4.0 g 6 g 9.3 g CE: comparison example
Example 11
[0270] Analogously to the conditions described under Examples 1a
and 5, different coated platelet-shaped copper-containing metal
pigments were produced. Rich pale gold G900 served as starting
material.
TABLE-US-00002 TABLE 2 Educt quantities of Examples 11-1 to 11-12
Procedure analogous to TEOS MEMO TMPTMA Example 11-1 1a, 5 17.5 g 1
g 16.8 g Example 11-2 1a, 5 21.8 g 1 g 16.8 g Example 11-3 1a, 5
26.0 g 1 g 16.8 g Example 11-4 1a, 5 32.8 g 1 g 16.8 g Example 11-5
1a, 5 62.0 g 1 g 16.8 g Example 11-6 1a, 5 32.8 g 1 g 29 g Example
11-7 1a, 5 62.0 g 1 g 29 g Example 11-8 1a, 5 77.5 g 1 g 29 g CE
11-9 1a, 5 32.8 g 1 g 4 g CE 11-10 1a, 5 62 g 1 g 11 g CE 11-11 1a,
5 5 g 1 g 16.8 g CE 11-12 1a, 5 5 g 1 g 29 g CE: comparison
example
Example 12
Application Example Powder Coating and Chemicals Test
[0271] The obtained pastes were dried under vacuum with a light
inert gas stream at 100.degree. C. and then sieved at 71-.mu.m mesh
size. The respective metallic effect pigment was incorporated
together with the powder coating AL 96 as well as with 0.2%
Aeroxide Alu C (from Evonik) by means of a ThermoMix for 4 minutes
on level 4. The pigmentation level was 5.0 wt.-%, as a verifiable
application behavior can be achieved with higher pigmentation.
[0272] The powder coating was therefore weighed out to 95.0 wt.-%.
The total quantity of powder coating in the mixer was 300 g plus
0.6 g Aeroxide Alu C. ThermoMix is a food processor customary in
the trade (from Vorwerk). The added Aeroxide Alu C is
Al.sub.2O.sub.3 particles which assume the function of an
anti-caking agent in this application case. The powder coatings
were applied using an OptiSelect (from ITWGema) in a powder
enclosure customary in the trade. To assess the application
properties, spraying was carried out into the powder compartment
for 20 seconds according to the parameters given in Table 1, then
the coating of the substrate was carried out and then the adhesion
to the electrodes and the adhesion to the baffle were comparatively
assessed. This method allows the long-term behavior of the pigments
to be assessed during practice-oriented varnishing.
[0273] Furthermore, the spray pattern was evaluated using the baked
powder coating. Attention was paid above all to the course, thus
the smoothness of the surface structure, as well as to black,
microscopically small defects, so-called black spots. Areas on the
powder coating surface which are brought about by an inhomogeneous
distribution of the metallic effect pigments are called black
spots. As these phenomena lie in the macroscopic range, the eye of
an expert in varnish technology is needed for the assessment of the
phenomenon. In particular very smooth structures with a very smooth
course without black spot phenomena are preferred.
[0274] The application behavior, the presence of black spots and
the structure or the course of the powder coatings were assessed
visually.
Chemicals Test
[0275] The coated test sheet was brought into a horizontal
position. 5 drops of 10% HCl were applied with exposure times of
180, 150, 120, 90, and 60 min. In addition, 5 drops of 1 M NaOH
were applied with exposure times of 180, 120, 60, 30 and 15
min.
[0276] The drops were then removed with water and the formerly
covered surfaces were compared visually with the uncovered
surfaces. Here, a rating scale of 0-3 (for each individual point)
was used (0=no attack, 3 maximum decomposition of pigments). The
ascertained points were then totaled.
TABLE-US-00003 TABLE 3 Chemicals test, powder coating SiO.sub.2
content Plastic content in Wt. ratio of SiO.sub.2 to Chemicals
Sample in wt.-% wt.-% plastic test CE: rich pale gold G900 -- -- --
18 CE: Example 1a 3.1 -- -- 18 Example 1b 3.1 17.6 1:5.7 0 Example
1c 3.1 22.3 1:7.2 0 CE: pale gold Dorolan L900 3.8 -- -- 11 pt.
Example 2, pale gold Dorolan 3.8 22.5 1:5.9 0 pt. L900 + plastic
layer CE: copper Dorolan L 900 3.1 -- -- 11 pt. Example 5: copper
Dorolan L 900 + 3.1 19.1 1:6.2 0 pt. plastic layer CE: fire red
Dorolan L 900 3.7 -- -- 20 pt. Example 6: fire red Dorolan L 900 +
3.7 19 1:5.1 0 pt. plastic layer Example 7: fire red Dorolan L 900
+ 3.7 13.6 1:3.7 0 pt. plastic layer CE: rich pale gold RBIG G900
-- -- -- 18 CE 8a: rich pale gold RBIG G900 + -- 23.6 -- 3 plastic
layer Example 8b: rich pale gold RBIG 9.8 23.6 1:2.4 0 G900 +
plastic layer + SiO.sub.2 CE: rich pale gold G900 -- -- 18 CE 9a:
rich pale gold G900 + -- 14.7 8 plastic layer Example 9b: rich pale
gold G900 + 3.3 14.7 1:4.5 0 plastic layer + SiO.sub.2 CE 10-1 3.3
5.7 1:1.7 14 CE 10-2 4.6 5.7 1:1.2 12 CE 10-3 6.0 5.7 1:1.0 13
Example 10-4 1.7* 13 1:7.6 0 Example 10-5 3.3 14.7 1:4.5 0 Example
10-6 1.2* 23.6 1:19.7 0 Example 10-7 3.0 23.6 1:7.9 0 Example 10-8
9.8 23.6 1:2.4 0 CE 10-9 -- 46 -- 0 CE 10-10 0.7* 30.2 1:43 0 CE
10-11 3.7 5 1:1.4 4 Example 11-1 2.0 16.2 1:8.1 0 Example 11-2 2.5
15.7 1:6.3 0 Example 11-3 3.0 16.7 1:5.6 0 Example 11-4 3.6 16.6
1:4.6 0 Example 11-5 6.7 16.2 1:2.4 0 Example 11-6 3.6 27.3 1:7.6 0
Example 11-7 6.6 26.7 1:4.0 0 Example 11-8 8.5 28.2 1:3.3 0 CE 11-9
3.6 4.6 1:1.3 5 CE 11-10 7.2 11 1:1.5 2 CE 11-11 0.8 16.7 1:20.9 4
CE: comparison example n.d. = not determined *theor. SiO.sub.2
content wt.-%: in each case relative to the uncoated
copper-containing metal pigment
Example 13
Application Example, Coil Coating and Chemicals Test
[0277] The pastes obtained in the above-named experiments were used
directly in the coil coating method. 8.0 g aluminum paste and 8.0 g
Solvesso 150 were thoroughly dispersed with a spatula until the
mixture was speck-free. 84.0 g PE varnish 42-00001 was then added
and the mixture stirred before being diluted with 5.0 g Solvesso
150. Stirring followed for 3 minutes at 500 rpm with a toothed ring
stirrer. The viscosity was 100''.+-.10 in a DIN4 cup.
[0278] This batch of varnish was drawn down on an alkane-aluminum
DIN: A4 sheet (No. 11) using a spiral doctor blade. The sheet was
immediately transferred into a furnace at 280.degree. for 55 sec.
Then the sheet was quenched in a water bath (RT). After 24 h at the
earliest, the chemicals test was then carried out.
[0279] The coated test sheet was brought into a horizontal
position. One drop each of hydrochloric acid (HCl) 5% and of
caustic soda solution (NaOH) 5% was applied to the sheet. The drop
size should be 20 to 25 mm in diameter. The drops were then covered
with a watch glass and left to stand for 48 h. The drops were then
removed with water and the formerly covered surfaces were compared
visually with the uncovered surfaces. Here, a rating scale of 0-3
was used (0=no attack, 3 maximum decomposition of pigments).
TABLE-US-00004 TABLE 4 Chemicals test, coil coating SiO.sub.2
content Plastic content Weight ratio of Chemicals in wt.-% in wt.-%
SiO.sub.2 to plastic test CE: rich pale -- -- -- 25 gold G900 CE:
1a 3.1 -- -- n.d. Example 1b 3.1 17.6 1:5.7 22 Example 1c 3.1 22.3
1:7.2 3 CE: comparison example wt.-%: in each case relative to the
uncoated copper-containing metal pigment
Example 14
Application Example, Powder Coating and Oxidation Test
[0280] Powder coating sheets were prepared from different
examples/comparison examples and cross-linked for 12 and optionally
also for 60 min at 200.degree. C. in a furnace. It was shown that
only in the case of Examples 8b, 9b, 10-5, 10-7 and 10-8 no color
change as a result of oxidation of the metallic effect pigments
occurred.
TABLE-US-00005 TABLE 5 Oxidation test, powder coatings Plastic
SiO.sub.2 Wt. ratio content content of SiO.sub.2 Oxida- Hue after
Hue after Sample in wt.-% in wt.-% to plastic tion 12 min 60 min
Starting color of the metal pigments: rich pale gold CE: rich pale
gold RBIG G900 -- -- -- yes dark n.d. CE 8a: rich pale gold RBIG
23.6 -- -- yes orange gold n.d. G900 + plastic layer Example 8b:
rich pale gold 23.6 9.8 1:2.4 no rich pale n.d. RBIG G900 + plastic
layer + gold SiO.sub.2 CE: rich pale gold G900 -- -- yes dark n.d.
CE 9a: rich pale gold G900 + 14.7 -- yes orange gold n.d. plastic
layer Example 9b: rich pale gold 14.7 3.3 1:4.5 no rich pale n.d.
G900 + plastic layer + SiO.sub.2 gold Starting color of the metal
pigments: pale gold CE: 8a -- 23.6 -- yes orange gold dark gold
Example: 10-5 14.7 3.3 1:4.5 no pale gold n.d. Example: 10-7 23.6
3.0 1:7.9 no pale gold n.d. Example: 10-8 23.6 9.8 1:2.4 no pale
gold pale gold CE: 10-9 46.0 -- -- yes orange gold dark gold CE:
10-10 30.2 0.7* 1:43 yes orange gold dark gold CE: 10-11 5 3.7
1:1.4 yes a little n.d. darker CE: comparison example n.d.: not
determined *theor. SiO.sub.2 content wt.-%: in each case relative
to the uncoated copper-containing metal pigment
[0281] Furthermore, experiments were carried out in which the state
of the oxidation was determined quantitatively by means of
colorimetry. Here, the powder coating was applied to sheets and
cross-linked for 10 min at 200.degree. C. in a furnace. The
lightness value (L value) of the obtained sheets was determined by
means of a Minolta Spectrophotometer CM-508i.
[0282] Furthermore, the color difference (.DELTA.L) as a result of
a treatment at 200.degree. C. lasting 60 min longer was determined
for different ones of the above-named powder coatings. The examples
according to the invention here showed a lightness deviation of
less than 3 units, while the comparison examples showed a lightness
deviation of more than 8 units, and thus a strong oxidation.
TABLE-US-00006 TABLE 6 Oxidation test, powder coatings,
determination by means of colorimetry Plastic SiO.sub.2 Wt. ratio
Ox- content content of SiO.sub.2 ida- L Sample in wt.-% in wt.-% to
plastic tion value .DELTA.L Example 11-1 2.0 16.2 1:8.1 no 62.7
-2.4 Example 11-2 2.5 15.7 1:6.3 no 62.6 -2.6 Example 11-3 3.0 16.7
1:5.6 no 63.7 n.d. Example 11-4 3.6 16.6 1:4.6 no 64.1 -2.5 Example
11-5 6.7 16.2 1:2.4 no 64.4 n.d. Example 11-6 3.6 27.3 1:7.6 no
63.3 n.d. Example 11-7 6.6 26.7 1:4.0 no 65.3 n.d. Example 11-8 8.5
28.2 1:3.3 no 64.2 n.d. CE 11-11 0.8 16.7 1:20.9 yes 61.4 -8.1 CE
11-12 0.7 27.9 1:39.9 yes 61.9 -8.4 CE: comparison example n.d.:
not determined wt.-%: in each case relative to the uncoated
copper-containing metal pigment
Example 15
Application Example Nail Polish
[0283] The metallic effect pigments were stirred with a
pigmentation of 4 wt.-% into base 359 (from International Lacquers)
with a brush and then transferred into nail polish bottles
customary in the trade. The nail polish bottles were then stored a)
at RT and b) in a furnace with a temperature of 40.degree. C. for 6
months. During the storage time, it was visually evaluated whether
a green discoloration set in. In addition, it was tested whether
the pigments which have settled at the bottom could be shaken up or
redispersed again. If either green discoloration occurred or if the
pigment could no longer be shaken up or redispersed, the storage
test was regarded as failed.
TABLE-US-00007 TABLE 7 Storage stability test, nail polish Plastic
SiO.sub.2 Storage content content in Wt. ratio of Storage stability
at in wt.-% wt.-% SiO.sub.2 to plastic stability at RT 40.degree.
C. CE: pale gold Dorolan -- 3.8 -- 10 days 3 days L900 Example 2:
pale gold 22.5 3.8 1:5.9 >6 months >6 months Dorolan L900 +
plastic layer CE: fire red Dorolan -- 3.7 -- 7 days 6 days L900
Example 3: fire red 19.0 3.7 1:5.1 >6 months >6 months
Dorolan L900 + plastic layer CE: copper Dorolan -- 3.1 -- 6 days 6
days L900 Example 4: copper 18.9 3.1 1:6.1 >6 months >6
months Dorolan L900 + plastic layer CE: comparison example wt.-%:
in each case relative to the uncoated copper-containing metal
pigment
[0284] It was shown that the SiO.sub.2 coating alone is unable to
guarantee a storage time of >6 months. Only by the additional
plastic layer could a storage stability of >6 months be
achieved.
Example 16
Application Example
Polymer
[0285] Different copper-containing metallic effect pigments were
processed, mixed with thermoplastic polypropylene (PP) (R 771-10;
from DOW, Germany, Wesseling), using the injection molding process
to form disks (surface area 42.times.60 mm, thickness 2 mm).
[0286] To produce a 1 wt.-% mixture, the process was as
follows:
[0287] 495 g polypropylene granules (PP) and 4.95 g of the
copper-containing pigment were mixed in a tumbling mixer and then
processed in a twin-screw extruder (from Bersdorff, Germany,
diameter 25 mm, 28UD) without the addition of further additives at
a processing temperature of approx. 230.degree. C. to form
granules. These granules were then processed by means of an
injection molding machine (Arburg Allrounder 221-55-250) at
260.degree. C. to form the sample platelets with the above-named
dimensions. The test for oxidation of the metal pigment took place
by comparing the hue of the above-named platelets with reference
platelets, the processing of which (production of granules and
injection molding) was carried out at 190.degree. C. For this, a
Byk-mac from Byk-Gardner was used, wherein a .DELTA.E<3 proved
oxidation stability.
TABLE-US-00008 TABLE 8 Application example - Oxidation test,
polymer Plastic SiO.sub.2 content content Wt. ratio in in of
SiO.sub.2 Sample wt.-% wt.-% to plastic Oxidation CE: rich pale
gold G900 -- -- -- yes CE: Example 1a -- 3.1 -- yes Example 1b 17.6
3.1 1:5.7 no CE: rich pale gold RBIG -- -- -- yes G900 CE 8a: rich
pale gold RBIG 23.6 -- -- yes G900 + plastic layer Example 8b: rich
pale gold 23.6 9.8 1:2.4 no RBIG G900 + plastic layer + SiO.sub.2
CE: comparison example wt.-%: in each case relative to the uncoated
copper-containing metal pigment
Example 17
Application Example Water-in-Silicone Body Lotion
TABLE-US-00009 [0288] TABLE 9 Application example -
Water-in-silicone body lotion Manufacturer/ INCI name Product name
wt.-% supplier Phase A Cyclopentasiloxane Dow Corning 1501 11.20
Dow Corning (and) Dimethiconol Cyclopentasiloxane Xiameter PMX-0245
5.75 Dow Corning Cyclosiloxane Cyclopentasiloxane Dow Corning 5225
C 13.80 Dow Corning (and) PEG/PPG-18/18 Dimethicone C 30-45 Alkyl
Dow Corning 3.45 Dow Corning Methicone Cosmetic Wax AMS-C30
Copper-containing 1.00 metal pigment according to Example 2 Phase B
Polysorbate 20 Tween 20 0.60 Croda Phenoxyethanol (and) Uniphen
P-23 0.35 Induchem Methylparaben (and) Ethylparaben (and)
Butylparaben (and) Probylparaben (and) Isobutylparaben Sodium
Chloride Sodium chloride 0.75 VWR Aqua Water 63.10
[0289] The copper-containing metallic effect pigment can be used in
a range of from 0.2 to 2.5 relative to the total weight of the
formulation. The balance can be made up with water.
[0290] Phase A was mixed and heated to 75.degree. C., Phase B was
heated to 70.degree. C. after mixing, then Phase B was added slowly
to Phase A accompanied by homogenization. Accompanied by stirring,
the emulsion was cooled and poured into an appropriate
container.
Example 18
Application Example
Eyeshadow Cream
TABLE-US-00010 [0291] TABLE 10 Application example - Eyeshadow
cream Manufacturer/ INCI name Product name wt.-% supplier Phase A
Castor Oil Castor oil 43.70 Honeywell Riedel-de Haen Ethylhexyl
Palmitate Cegesoft C24 6.00 Cognis Cocos Nucifera Lipovol C-76 7.00
Lipo Chemicals (Coconut) Oil Cera Alba Ewacera 12 6.00 H. Erhard
Wagner Isopropyl Lanolate Ewalan IP 5.00 H. Erhard Wagner Persea
Gratissima Avocado Butter 7.00 Impag (Avocado) Oil and Hydrogenated
Vegetable Oil Magnesium Stearate Magnesium stearate 3.00
Sigma-Aldrich Bis-Hydroxyethoxypropyl Dow Corning 5562 7.00 Dow
Corning Dimethicone Carbinol Fluid Dimethicone/Vinyl Dow Corning
9701 5.00 Dow Corning Dimethicone Cosmetic Powder Crosspolymer and
Silica Phenoxyethanol (and) Uniphen P-23 0.30 Induchem
Methylparaben (and) Ethylparaben (and) Butylparaben (and)
Probylparaben (and) Isobutylparaben Phase B Copper-containing metal
10.00 pigment according to Example 3
[0292] The pigment can be used in a range of from 5 to 22.0 wt.-%,
relative to the total weight of the formulation. The balance can be
made up with castor oil.
[0293] Phase A was mixed and heated to 85.degree. C., Phase B was
then added to Phase A accompanied by stirring. After being poured
into a corresponding container, the mixture is cooled to room
temperature.
Example 19
Application Example
Shower Gel
TABLE-US-00011 [0294] TABLE 11 Application example - Shower gel
wt.- Manufacturer/ INCI name Product name % supplier Phase A
Copper-containing 0.50 metal pigment according to Example 3 Aqua
Water 58.10 Acrylates Copolymer Carbopol Aqua SF-1 5.50 Lubrizol
Phase B Sodium Hydroxide NaOH (10 wt.-%) 1.50 Phase C Sodium
Laureth Texapon NSO 22.00 Cognis Sulfate Cocamidopropyl Tego Betain
F 50 6.00 Evonik Betaine PEG-7 Glyceryl Emanon HE 2.00 Kao Corp.
Cocoate Disodium Laureth Sectacin 103 Spezial 2.00 Zschimmmer
Sulfosuccinate & Schwarz Phase D Phenoxyethanol (and) Nipaguard
PO 5 0.60 Clariant Piroctone Olamine Fragrance Water Lily OA 0.20
Bell Flavors and Fragrances Sodium Chloride Sodium chloride 1.60
VWR
[0295] The pigment can be used in a range of from 0.01 to 1.0
wt.-%, relative to the total weight of the formulation. The balance
can be made up with water.
[0296] Phase A was mixed and stirred. Phase B was then added and
stirred until a homogeneous appearance was achieved. Phase C was
weighed out separately, mixed and added to Phase AB. The mixture
can then be stirred again and Phase D was added individually.
Example 20
Application Example
Pressed Eyeshadow
TABLE-US-00012 [0297] TABLE 12 Application example - Pressed
eyeshadow Manufacturer/ INCI name Product name wt.-% Supplier Phase
A Mica Silk Mica 17.00 VWR Boron Nitride Softouch CCS 102 2.50
Momentive Zinc Stearate Zinc stearate 7.00 VWR Talc Talcum powder
43.50 Sigma-Aldrich Copper-containing metal 20.00 pigment according
to Example 3 Phase B Dimethicone Xiameter PMX-200 5.00 Dow Corning
Silicone Fluid 5cs Cyclopentasiloxane Dow Corning 9040 5.00 Dow
Corning (and) Dimethicone Elastomer Crosspolymer
[0298] The pigment can be used in a range of from 5.0 to 40.0
wt.-%, relative to the total weight of the formulation. The balance
can be made up with talc.
[0299] Phase A was mixed for 30 s at 2500 rpm in a high-speed
mixer. Phase B was then added and the mixture mixed for 60 s at
3000 rpm in the same mixer. Lastly, the powder mixture is pressed
into shape by means of an eyeshadow press at 150 bar for 30 s.
Example 21
Application Example
Hair Mascara
TABLE-US-00013 [0300] TABLE 13 Application example - Hair mascara
Manufacturer/ INCI name Product name wt.-% supplier Phase A
Polyquaternium-16 Luviquat FC 905 2.70 BASF (Luviquat Exellence)
Propylene glycol 1,2-propanediol 1.80 VWR Methylparaben Methyl-4-
0.20 Sigma-Aldrich hydroxybenzoate Aqua Water 64.45 Phase B
Cetearyl Alcohol Lanette O 5.00 Cognis Dimethicone Xiameter PMX-200
1.00 Dow Corning Silicone Fluid 350cs Ceteareth-25 Cremophor A 25
2.00 BASF Propylparaben Propyl-4- 0.10 Sigma-Aldrich
hydroxybenzoate Phase C Hydroxypropylcellulose Klucel G 0.50
Ashland Magnesium Aluminium Veegum HV 0.50 R. T. Silicate
Vanderbilt Aqua Water 19.00 Phase D Copper-containing 2.50 metal
pigment according to Example 3 Phenoxyethanol (and) Phenonip 0.20
Clariant Methylparaben (and) Butylparaben (and) Ethylparaben (and)
Propylparaben (and) Isobutylparaben Fragrance Blue Shadow OKO 0.05
Bell Flavors and Fragrances
[0301] The pigment can be used in a range of from 1.0 to 10.0
wt.-%, relative to the total weight of the formulation. The balance
can be made up with the water from Phase A.
[0302] Phase A and Phase B were heated separately to 80.degree. C.,
then Phase B was slowly added to Phase A. In a separate vessel,
Klucel and Veegum were added to the water from Phase C. Phase AB
was then cooled to 40.degree. C. and, during the cooling, Phases C
and D were added accompanied by stirring.
Example 22
Application Example Hair gel
TABLE-US-00014 [0303] TABLE 14 Application example - Hair gel
Manufacturer/ INCI name Product name wt.-% supplier Phase A
Copper-containing 0.10 metal pigment according to Example 2
Ammonium Aristoflex AVC 1.40 Clariant Acryloyldimethyltaurate/ VP
Copolymer Citric Acid Citric acid 0.10 VWR Aqua Water 55.10 Phase B
PVP Luviskol K 30 1.50 BASF Powder Propylene Glycol, Germaben II
0.20 International Diazolidinyl, Urea, Speciality Methylparaben,
Products Propylparaben Triethanolamine Triethanolamine 1.20 VWR
Water Water 40.40
[0304] The pigment can be used in a range of from 0.01 to 2.0
wt.-%, relative to the total weight of the formulation. The balance
can be made up with water.
[0305] The pigment was stirred with water from Phase A, Aristoflex
AVC and citric acid were added accompanied by stirring and mixed at
a speed of 800 rpm for 15 minutes. Phase B was dissolved until a
homogeneous solution formed, then Phase B was added to Phase A and
mixed.
Example 23
Application Example
Body Powder
TABLE-US-00015 [0306] TABLE 15 Application example - Body powder
Manufacturer/ INCI name Product name wt.-% supplier Phase A Mica
Silk Mica 58.70 VWR Talc Talcum powder 18.00 Sigma-Aldrich Boron
Nitride Softouch CCS 102 5.00 Advanced Ceramics Nylon-12 Orgasol
2002 D/Nat 8.00 Arkema Magnesium Stearate Magnesium stearate 6.00
Sigma-Aldrich Methylparaben, Rokonsal SSH-1 0.30 ISP Biochema
Propylparaben Copper-containing 2.00 metal pigment according to
Example 2 Phase B Tridecyl Stearate Lipovol MOS-130 2.00 Lipo
Chemicals (and) Tridecyl Trimellitate (and) Dipentaerythrityl
Hexacaprylate/ Hexacaprate
[0307] The pigment can be used in a range of from 0.2 to 5.0 wt.-%,
relative to the total weight of the formulation. The balance can be
made up with silk mica.
[0308] Phase A was mixed, then Phase B was added to Phase A and the
mixture was then poured into a suitable vessel.
Example 24
Application Example
Lip Gloss
TABLE-US-00016 [0309] TABLE 16 Application example - Lip gloss
Manufacturer/ INCI name Product name wt.-% supplier Phase A
Hydrogenated Versagel ME 750 79.00 Calumet Penreco Polyisobutene
(and) Ethylene/Propylene/ Styrene Copolymer (and)
Butylene/Ethylene/ Styrene Copolymer Simmondsia Chinensis Jojoba
Oil - 2.00 BioChemica (Jojoba) Seed Oil Natural/Golden Caprylyl
Trimethicone Silcare Silicone 7.00 Clariant 31M50 Stearyl
Dimethicone Silcare Silicone 3.20 Clariant 41M65 Hydrogenated
Nexbase 2002 4.00 Jan Dekker Polydecene Isopropyl Myristate
Isopropyl myristate 4.50 VWR Phase B Copper-containing 0.10 metal
pigment according to Example 2 Propylparaben Propyl-4- 0.20
Sigma-Aldrich hydroxybenzoate
[0310] The pigment can be used in a range of from 0.10 to 8.00
wt.-%, relative to the total weight of the formulation. The balance
can be made up with Versagel ME 750.
[0311] Phase A was heated to 85.degree. C., then the contents of
Phase B were added individually to Phase A, followed by stirring
until a uniform consistency formed and then pouring into a lip
gloss container.
Example 25
Application Example
Lip Liner
TABLE-US-00017 [0312] TABLE 17 Application example - Lip liner
Manufacturer/ INCI name Product name wt.-% supplier Phase A
Hydrogenated Coco- Softisan 100 12.35 Sasol Wax Glycerides
Candelilla Cera Ewacera 42 14.00 H. Erhard Wagner Magnesium
Stearate Magnesium stearate 6.00 Sigma-Aldrich Stearic Acid
Kortacid 1895 8.50 Akzo Nobel Hydrogenated Lipex 401 8.00 Aarhus
Karlshamn Coconut Oil Cetyl Palmitate Kahlwax 7157 7.00 Kahl
Caprylic/Capric Liponate GC-K 3.60 Lipo Chemicals Triglyceride
Soybean Glycerides Lipex L'sens 15.00 Aarhus Karlshamn (and)
Butyrospermum Parkii Tocopheryl Acetate dl-alpha-Tocopheryl 0.25
Jan Dekker acetate Methylparaben; Rokonsal SSH-1 0.30 ISP Biochema
Propylparaben Phase B Copper-containing 25.00 metal pigment
according to Example 3
[0313] The pigment can be used in a range of from 15 to 25 wt.-%,
relative to the total weight of the formulation. Alternatively,
further color and/or effect pigments in addition to the pigment can
be added. The maximum pigmentation level should, however, not be
exceeded.
[0314] Phase A was heated to 85.degree. C. and then Phase B was
added to Phase A accompanied by stirring until a uniform material
resulted. The mixture was then poured, hot, into a pencil mold.
Example 26
Application Example
Lipstick
TABLE-US-00018 [0315] TABLE 18 Application example - Lipstick
Manufacturer/ INCI name Product name wt.-% supplier Phase A
Carnauba Wax Ewacera 34 4.50 H. Erhard Wagner Cera Alba Ewacera 12
3.50 H. Erhard Wagner Candelilla Cera Ewacera 42 4.00 H. Erhard
Wagner Extract Microcrystalline TeCero-Wax 1030 K 7.20 TH.C. Tromm
Wax Cetyl Palmitate Kahlwax 7157 2.00 Kahl Hydrogenated Softisan
100 5.00 Sasol Wax Coco-Glycerides Petrolatum Penreco Blond 5.80
Calumet Penreco Cetearyl Luvitol EHO 10.70 BASF Ethylhexanoate
Tocopheryl dl-alpha-tocopheryl 0.50 Jan Dekker Acetate acetate
Castor Oil Castor oil 46.60 Honeywel Riedel-de Haen Phase B
Copper-containing 10.00 metal pigment according to Example 2
Methylparaben, Rokonsal SSH-1 0.20 ISP Biochema Propylparaben
[0316] The pigment can be used in a range of from 0.5 to 21.0
wt.-%, relative to the total weight of the formulation. The balance
can be made up with castor oil.
[0317] Phase A was heated to 85.degree. C., then Phase B was added
to Phase A and mixed. This mixture was then poured, at a
temperature of 75.degree. C., into a lipstick mold.
Example 27
Application Example
Liquid Eyeliner
TABLE-US-00019 [0318] TABLE 19 Application example - Liquid
eyeliner Manufacturer/ INCI name Product name wt.-% supplier Phase
A Aqua Water 66.70 Water/carbon black MBD 201 3.00 Geotech
dispersion Acrylates Copolymer Covacryl E14 10.00 LCW Magnesium
Veegum HV 1.00 C. H. Erbsloh Aluminium Silicate Phase B Propylene
Glycol 1,2-propanediol 3.00 VWR Triethanolamine Triethanolamine
1.40 VWR Phase C Xanthan Gum Keltrol CG-T 0.30 CP Kelco Phase D
Copper-containing 3.00 metal pigment according to Example 3 Mica
Silk Mica 2.00 VWR Phase E Stearic Acid Kortacid 1895 2.80 Akzo
Nobel Glyceryl Stearate Aldo MS K FG 0.80 Lonza Oleyl Alcohol
HD-Ocenol 90/95 V 0.50 Cognis Phenoxyethanol (and) Uniphen P-23
0.50 Induchem Methylparaben (and) Ethylparaben (and) Butylparaben
(and) Probylparaben (and) Isobutylparaben Phase F Dimethicone (and)
Xiameter PMX-1184 5.00 Dow Corning Trisiloxane Silicone Fluid
[0319] The pigment can be used in a range of from 0.5 to 8.0 wt.-%,
relative to the total weight of the formulation. The balance can be
made up with water.
[0320] Veegum was dispersed in Phase A and stirred for 15 minutes,
then Phase B was added to Phase A, then Phase C to Phase AB and
stirred again for 10 minutes. Phase D was then added to Phase ABC
and heated to 75.degree. C. Next, phase E was also heated to
75.degree. C. and added to Phase ABCD. After cooling to 60.degree.
C., Phase F was added and the mixture poured into a suitable
vessel.
Example 28
Application Example
Mousse
TABLE-US-00020 [0321] TABLE 20 Application example - Mousse INCI
name Product name wt.-% Manufacturer/supplier Phase A
Cyclopentasiloxane Xiameter PMX-0245 8.60 Dow Corning Cyclosiloxane
Hydrogenated MC 30 4.00 www.sophim.com Polyisobutene Dimethicone
(and) Dow Corning 9041 37.14 Dow Corning Dimethicone Crosspolymer
Silicone Elastomer Blend Squalane Squalane 5.74 Impag Isononyl
Isononanoate Dermol 99 10.16 Alzo International Hydrogenated Jojoba
Oil Jojoba Butter LM 2.15 Desert Whale Hydrogenated Jojaba Oil
Jojoba Butter HM 1.00 Desert Whale C30-45 Alkyl Methicone Dow
Corning AMS-C30 1.15 Dow Corning (and) C30-45 Olefin Cosmetic Wax
Stearyl Dimethicone Dow Corning 2503 0.47 Dow Corning Cosmetic Wax
Cyclopentasiloxane (and) Dow Corning 670 Fluid 5.00 Dow Corning
Polypropylsilsesquioxane Phase B Dimethicone/Vinyl Dow Corning 9506
16.02 Dow Corning Dimethicone Crosspolymer Powder Silica Dimethyl
Silylate Covasilic 15 0.17 LCW Talc Talcum powder 5.00
Sigma-Aldrich Copper-containing 3.00 metal pigment according to
Example 2 Phase D Propylene Glycol, Germaben II 0.40 International
Speciality Diazolidinyl Urea, Products Methylparaben,
Propylparaben
[0322] The pigment can be used in a range of from 0.1 to 8.0 wt.-%,
relative to the total weight of the formulation. The balance can be
made up with Dow Corning 9041 elastomer.
[0323] Phase A was mixed and heated until everything had melted.
Phase B was weighed out separately and mixed with a high-speed
mixer for 60 s at 2400 rpm. Half of the melted Phase A was added to
Phase B and mixed again in the mixer at 2400 rpm for 30 s. Then,
the remaining part of Phase B was also added to Phase A and mixed
again at 2400 rpm for 30 s. Lastly, Phase C is added to Phase AB
and mixed again at 2400 rpm for 30 s in the high-speed mixer.
Example 29
Application Example
Nail Polish
TABLE-US-00021 [0324] TABLE 21 Application example - Nail polish
wt.- Manufacturer/ INCI name Product name % supplier Phase A
Copper-containing 2.00 metal pigment according to Example 2 Phase B
Butyl Acetate (and) Ethyl International 98.00 International Acetate
(and) Nitrocellulose Lacquers Nailpolish Lacquers (and) Isopropyl
Alcohol & Care Base 359
[0325] The pigment can be used in a range of from 0.1 to 10.0
wt.-%, relative to the total weight of the formulation. The balance
can be made up with International Lacquers nail polish.
[0326] Phase A and Phase B were mixed and then poured into an
appropriate container.
Example 30
Application Example
Nail Polish with "Soft Touch" Effect
TABLE-US-00022 [0327] TABLE 22 Application example - Nail polish
with "soft touch" effect wt.- Manufacturer/ INCI name Product name
% supplier Phase A Copper-containing 2.00 metal pigment according
to Example 2 Ceraflour 913 5.00 Byk Chemie Phase B Butyl Acetate
(and) Ethyl International 93.00 International Acetate (and)
Nitrocellulose Lacquers Nailpolish Lacquers (and) Isopropyl Alcohol
& Care Base 359
[0328] The pigment can be used in a range of from 0.1 to 10.0
wt.-%, relative to the total weight of the formulation. The balance
can be made up with International Lacquers nail polish.
Example 31
Application Example
Aqueous Nail Polish
[0329] The pigment can be used in an aqueous nail polish according
to WO 2007/115675 A2, Example 1. The pigmentation level here is 0.1
to 10.0 wt.-%, for example 1.5 wt.-%, relative to the total weight
of the formulation.
Example 32
Application Example
Liquid Eyeshadow
TABLE-US-00023 [0330] TABLE 23 Application example - Liquid
eyeshadow Manufacturer/ INCI name Product name wt.-% supplier Phase
A Water Water 70.10 Glycerin Pricerine 9090 6.00 Croda Phase B
PEG-800 Polyglycol 35000 S 0.60 Clariant Allantoin Allantoin 0.30
3V Ammonium Aristoflex AVC 0.80 Clariant Acryloyldimethyltaurate/
VP Copolymer Acrylates Copolymer Worlee Micromer 5.00 Worlee CEK
20/50 Phase C Copper-containing 10.00 metal pigment according to
Example 2 Divinyldimethicone/ Dow Corning HMW 6.00 Dow Corning
Dimethicone 2220 Non-Ionic Copolymer C12-C13 Emulsion Pareth-3,
C12-C13 Pareth-23 Fragrance Water Lily OA 0.20 Bell Flavors and
Fragrances Phenoxyethanol (and) Phenonip 1.00 Clariant
Methylparaben (and) Butylparaben (and) Ethylparaben (and)
Propylparaben (and) Isobutylparaben
[0331] The pigment can be used in a range of from 0.10 to 17.00
wt.-%. The balance can be made up with water.
[0332] Phase A was stirred, then the contents of Phase B were added
individually to Phase A and stirred until a uniform consistency
formed. The contents of Phase C were then added individually to
Phase AB and stirred until a uniform consistency formed again.
* * * * *
References